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Atom
Helium atom ground state
An illustration of the helium atom, depicting the nucleus (pink) and the electron cloud distribution (black). The nucleus (upper right) in helium-4 is in reality spherically symmetric and closely resembles the electron cloud, although for more complicated nuclei this is not always the case. The black bar is one angstrom (10−10 m or 100 pm).
Classification
Smallest recognized division of a chemical element
Properties
Mass range1.67×10−27 to 4.52×10−25 kg
Electric chargezero (neutral), or ion charge
Diameter range62 pm (He) to 520 pm (Cs) (data page)
ComponentsElectrons and a compact nucleus of protons and neutrons

Atoms are the basic particles of the chemical elements and the fundamental building blocks of matter. An atom consists of a nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished from each other by the number of protons that are in their atoms. For example, any atom that contains 11 protons is sodium, and any atom that contains 29 protons is copper. Atoms with the same number of protons but a different number of neutrons are called isotopes of the same element.

Atoms are extremely small, typically around 100 picometers across. A human hair is about a million carbon atoms wide. Atoms are smaller than the shortest wavelength of visible light, which means humans cannot see atoms with conventional microscopes. They are so small that accurately predicting their behavior using classical physics is not possible due to quantum effects.

More than 99.94%[1] of an atom's mass is in the nucleus. Protons have a positive electric charge and neutrons have no charge, so the nucleus is positively charged. The electrons are negatively charged, and this opposing charge is what binds them to the nucleus. If the numbers of protons and electrons are equal, as they normally are, then the atom is electrically neutral as a whole. A charged atom is called an ion. If an atom has more electrons than protons, then it has an overall negative charge and is called a negative ion (or anion). Conversely, if it has more protons than electrons, it has a positive charge and is called a positive ion (or cation).

The electrons of an atom are attracted to the protons in an atomic nucleus by the electromagnetic force. The protons and neutrons in the nucleus are attracted to each other by the nuclear force. This force is usually stronger than the electromagnetic force that repels the positively charged protons from one another. Under certain circumstances, the repelling electromagnetic force becomes stronger than the nuclear force. In this case, the nucleus splits and leaves behind different elements. This is a form of nuclear decay.

Atoms can attach to one or more other atoms by chemical bonds to form chemical compounds such as molecules or crystals. The ability of atoms to attach and detach from each other is responsible for most of the physical changes observed in nature. Chemistry is the science that studies these changes.

History of atomic theory

[edit]

In philosophy

[edit]

The basic idea that matter is made up of tiny indivisible particles is an old idea that appeared in many ancient cultures. The word atom is derived from the ancient Greek word atomos,[a] which means "uncuttable". But this ancient idea was based in philosophical reasoning rather than scientific reasoning. Modern atomic theory is not based on these old concepts.[2][3] In the early 19th century, the scientist John Dalton found evidence that matter really is composed of discrete units, and so applied the word atom to those units.[4]

Dalton's law of multiple proportions

[edit]
Various atoms and molecules from A New System of Chemical Philosophy (John Dalton 1808).

In the early 1800s, John Dalton compiled experimental data gathered by him and other scientists and discovered a pattern now known as the "law of multiple proportions". He noticed that in any group of chemical compounds which all contain two particular chemical elements, the amount of Element A per measure of Element B will differ across these compounds by ratios of small whole numbers. This pattern suggested that each element combines with other elements in multiples of a basic unit of weight, with each element having a unit of unique weight. Dalton decided to call these units "atoms".[5]

For example, there are two types of tin oxide: one is a grey powder that is 88.1% tin and 11.9% oxygen, and the other is a white powder that is 78.7% tin and 21.3% oxygen. Adjusting these figures, in the grey powder there is about 13.5 g of oxygen for every 100 g of tin, and in the white powder there is about 27 g of oxygen for every 100 g of tin. 13.5 and 27 form a ratio of 1:2. Dalton concluded that in the grey oxide there is one atom of oxygen for every atom of tin, and in the white oxide there are two atoms of oxygen for every atom of tin (SnO and SnO2).[6][7]

Dalton also analyzed iron oxides. There is one type of iron oxide that is a black powder which is 78.1% iron and 21.9% oxygen; and there is another iron oxide that is a red powder which is 70.4% iron and 29.6% oxygen. Adjusting these figures, in the black powder there is about 28 g of oxygen for every 100 g of iron, and in the red powder there is about 42 g of oxygen for every 100 g of iron. 28 and 42 form a ratio of 2:3. Dalton concluded that in these oxides, for every two atoms of iron, there are two or three atoms of oxygen respectively. These substances are known today as iron(II) oxide and iron(III) oxide, and their formulas are FeO and Fe2O3 respectively. Iron(II) oxide's formula is normally written as FeO, but since it is a crystalline substance we could alternately write it as Fe2O2, and when we contrast that with Fe2O3, the 2:3 ratio for the oxygen is plain to see.[8][9]

As a final example: nitrous oxide is 63.3% nitrogen and 36.7% oxygen, nitric oxide is 44.05% nitrogen and 55.95% oxygen, and nitrogen dioxide is 29.5% nitrogen and 70.5% oxygen. Adjusting these figures, in nitrous oxide there is 80 g of oxygen for every 140 g of nitrogen, in nitric oxide there is about 160 g of oxygen for every 140 g of nitrogen, and in nitrogen dioxide there is 320 g of oxygen for every 140 g of nitrogen. 80, 160, and 320 form a ratio of 1:2:4. The respective formulas for these oxides are N2O, NO, and NO2.[10][11]

Discovery of the electron

[edit]

In 1897, J. J. Thomson discovered that cathode rays can be deflected by electric and magnetic fields, which meant that cathode rays are not a form of light but made of electrically charged particles, and their charge was negative given the direction the particles were deflected in.[12] He measured these particles to be 1,700 times lighter than hydrogen (the lightest atom).[13] He called these new particles corpuscles but they were later renamed electrons since these are the particles that carry electricity.[14] Thomson also showed that electrons were identical to particles given off by photoelectric and radioactive materials.[15] Thomson explained that an electric current is the passing of electrons from one atom to the next, and when there was no current the electrons embedded themselves in the atoms. This in turn meant that atoms were not indivisible as scientists thought. The atom was composed of electrons whose negative charge was balanced out by some source of positive charge to create an electrically neutral atom. Ions, Thomson explained, must be atoms which have an excess or shortage of electrons.[16]

Discovery of the nucleus

[edit]
The Rutherford scattering experiments: The extreme scattering of some alpha particles suggested the existence of a nucleus of concentrated charge.

The electrons in the atom logically had to be balanced out by a commensurate amount of positive charge, but Thomson had no idea where this positive charge came from, so he tentatively proposed that it was everywhere in the atom, the atom being in the shape of a sphere. This was the mathematically simplest hypothesis to fit the available evidence, or lack thereof. Following from this, Thomson imagined that the balance of electrostatic forces would distribute the electrons throughout the sphere in a more or less even manner.[17] Thomson's model is popularly known as the plum pudding model, though neither Thomson nor his colleagues used this analogy.[18] Thomson's model was incomplete, it was unable to predict any other properties of the elements such as emission spectra and valencies. It was soon rendered obsolete by the discovery of the atomic nucleus.

Between 1908 and 1913, Ernest Rutherford and his colleagues Hans Geiger and Ernest Marsden performed a series of experiments in which they bombarded thin foils of metal with a beam of alpha particles. They did this to measure the scattering patterns of the alpha particles. They spotted a small number of alpha particles being deflected by angles greater than 90°. This shouldn't have been possible according to the Thomson model of the atom, whose charges were too diffuse to produce a sufficiently strong electric field. The deflections should have all been negligible. Rutherford proposed that the positive charge of the atom is concentrated in a tiny volume at the center of the atom and that the electrons surround this nucleus in a diffuse cloud. This nucleus carried almost all of the atom's mass. Only such an intense concentration of charge, anchored by its high mass, could produce an electric field that could deflect the alpha particles so strongly.[19]

Bohr model

[edit]
The Bohr model of the atom, with an electron making instantaneous "quantum leaps" from one orbit to another with gain or loss of energy. This model of electrons in orbits is obsolete.

A problem in classical mechanics is that an accelerating charged particle radiates electromagnetic radiation, causing the particle to lose kinetic energy. Circular motion counts as acceleration, which means that an electron orbiting a central charge should spiral down into that nucleus as it loses speed. In 1913, the physicist Niels Bohr proposed a new model in which the electrons of an atom were assumed to orbit the nucleus but could only do so in a finite set of orbits, and could jump between these orbits only in discrete changes of energy corresponding to absorption or radiation of a photon.[20] This quantization was used to explain why the electrons' orbits are stable and why elements absorb and emit electromagnetic radiation in discrete spectra.[21] Bohr's model could only predict the emission spectra of hydrogen, not atoms with more than one electron.

Discovery of protons and neutrons

[edit]

Back in 1815, William Prout observed that the atomic weights of many elements were multiples of hydrogen's atomic weight, which is in fact true for all of them if one takes isotopes into account. In 1898, J. J. Thomson found that the positive charge of a hydrogen ion is equal to the negative charge of an electron, and these were then the smallest known charged particles.[22] Thomson later found that the positive charge in an atom is a positive multiple of an electron's negative charge.[23] In 1913, Henry Moseley discovered that the frequencies of X-ray emissions from an excited atom were a mathematical function of its atomic number and hydrogen's nuclear charge. In 1919, Rutherford bombarded nitrogen gas with alpha particles and detected hydrogen ions being emitted from the gas, and concluded that they were produced by alpha particles hitting and splitting the nuclei of the nitrogen atoms.[24]

These observations led Rutherford to conclude that the hydrogen nucleus is a singular particle with a positive charge equal to the electron's negative charge.[25] He named this particle "proton" in 1920.[26] The number of protons in an atom (which Rutherford called the "atomic number"[27][28]) was found to be equal to the element's ordinal number on the periodic table and therefore provided a simple and clear-cut way of distinguishing the elements from each other. The atomic weight of each element is higher than its proton number, so Rutherford hypothesized that the surplus weight was carried by unknown particles with no electric charge and a mass equal to that of the proton.

In 1928, Walter Bothe observed that beryllium emitted a highly penetrating, electrically neutral radiation when bombarded with alpha particles. It was later discovered that this radiation could knock hydrogen atoms out of paraffin wax. Initially it was thought to be high-energy gamma radiation, since gamma radiation had a similar effect on electrons in metals, but James Chadwick found that the ionization effect was too strong for it to be due to electromagnetic radiation, so long as energy and momentum were conserved in the interaction. In 1932, Chadwick exposed various elements, such as hydrogen and nitrogen, to the mysterious "beryllium radiation", and by measuring the energies of the recoiling charged particles, he deduced that the radiation was actually composed of electrically neutral particles which could not be massless like the gamma ray, but instead were required to have a mass similar to that of a proton. Chadwick now claimed these particles as Rutherford's neutrons.[29]

The current consensus model

[edit]
The modern model of atomic orbitals draws zones where an electron is most likely to be found at any moment.

In 1925, Werner Heisenberg published the first consistent mathematical formulation of quantum mechanics (matrix mechanics).[30] One year earlier, Louis de Broglie had proposed that all particles behave like waves to some extent,[31] and in 1926 Erwin Schrödinger used this idea to develop the Schrödinger equation, which describes electrons as three-dimensional waveforms rather than points in space.[32] A consequence of using waveforms to describe particles is that it is mathematically impossible to obtain precise values for both the position and momentum of a particle at a given point in time. This became known as the uncertainty principle, formulated by Werner Heisenberg in 1927.[30] In this concept, for a given accuracy in measuring a position one could only obtain a range of probable values for momentum, and vice versa.[33] Thus, the planetary model of the atom was discarded in favor of one that described atomic orbital zones around the nucleus where a given electron is most likely to be found.[34][35] This model was able to explain observations of atomic behavior that previous models could not, such as certain structural and spectral patterns of atoms larger than hydrogen.

Structure

[edit]

Subatomic particles

[edit]

Though the word atom originally denoted a particle that cannot be cut into smaller particles, in modern scientific usage the atom is composed of various subatomic particles. The constituent particles of an atom are the electron, the proton, and the neutron.

The electron is the least massive of these particles by four orders of magnitude at 9.11×10−31 kg, with a negative electrical charge and a size that is too small to be measured using available techniques.[36] It was the lightest particle with a positive rest mass measured, until the discovery of neutrino mass. Under ordinary conditions, electrons are bound to the positively charged nucleus by the attraction created from opposite electric charges. Electrons have been known since the late 19th century, mostly thanks to J.J. Thomson; see history of subatomic physics for details.

Protons have a positive charge and a mass of 1.6726×10−27 kg. The number of protons in an atom is called its atomic number. Ernest Rutherford (1919) observed that nitrogen under alpha-particle bombardment ejects what appeared to be hydrogen nuclei. By 1920 he had accepted that the hydrogen nucleus is a distinct particle within the atom and named it proton.

Neutrons have no electrical charge and have a mass of 1.6749×10−27 kg.[37][38] Neutrons are the heaviest of the three constituent particles, but their mass can be reduced by the nuclear binding energy. Neutrons and protons (collectively known as nucleons) have comparable dimensions—on the order of 2.5×10−15 m—although the 'surface' of these particles is not sharply defined.[39] The neutron was discovered in 1932 by the English physicist James Chadwick.

In the Standard Model of physics, electrons are truly elementary particles with no internal structure, whereas protons and neutrons are composite particles composed of elementary particles called quarks. There are two types of quarks in atoms, each having a fractional electric charge. Protons are composed of two up quarks (each with charge +2/3) and one down quark (with a charge of −1/3). Neutrons consist of one up quark and two down quarks. This distinction accounts for the difference in mass and charge between the two particles.[40][41]

The quarks are held together by the strong interaction (or strong force), which is mediated by gluons. The protons and neutrons, in turn, are held to each other in the nucleus by the nuclear force, which is a residuum of the strong force that has somewhat different range-properties (see the article on the nuclear force for more). The gluon is a member of the family of gauge bosons, which are elementary particles that mediate physical forces.[40][41]

Nucleus

[edit]
The binding energy needed for a nucleon to escape the nucleus, for various isotopes

All the bound protons and neutrons in an atom make up a tiny atomic nucleus, and are collectively called nucleons. The radius of a nucleus is approximately equal to  femtometres, where is the total number of nucleons.[42] This is much smaller than the radius of the atom, which is on the order of 105 fm. The nucleons are bound together by a short-ranged attractive potential called the residual strong force. At distances smaller than 2.5 fm this force is much more powerful than the electrostatic force that causes positively charged protons to repel each other.[43]

Atoms of the same element have the same number of protons, called the atomic number. Within a single element, the number of neutrons may vary, determining the isotope of that element. The total number of protons and neutrons determine the nuclide. The number of neutrons relative to the protons determines the stability of the nucleus, with certain isotopes undergoing radioactive decay.[44]

The proton, the electron, and the neutron are classified as fermions. Fermions obey the Pauli exclusion principle which prohibits identical fermions, such as multiple protons, from occupying the same quantum state at the same time. Thus, every proton in the nucleus must occupy a quantum state different from all other protons, and the same applies to all neutrons of the nucleus and to all electrons of the electron cloud.[45]

A nucleus that has a different number of protons than neutrons can potentially drop to a lower energy state through a radioactive decay that causes the number of protons and neutrons to more closely match. As a result, atoms with matching numbers of protons and neutrons are more stable against decay, but with increasing atomic number, the mutual repulsion of the protons requires an increasing proportion of neutrons to maintain the stability of the nucleus.[45]

Illustration of a nuclear fusion process that forms a deuterium nucleus, consisting of a proton and a neutron, from two protons. A positron (e+)—an antimatter electron—is emitted along with an electron neutrino.

The number of protons and neutrons in the atomic nucleus can be modified, although this can require very high energies because of the strong force. Nuclear fusion occurs when multiple atomic particles join to form a heavier nucleus, such as through the energetic collision of two nuclei. For example, at the core of the Sun protons require energies of 3 to 10 keV to overcome their mutual repulsion—the coulomb barrier—and fuse together into a single nucleus.[46] Nuclear fission is the opposite process, causing a nucleus to split into two smaller nuclei—usually through radioactive decay. The nucleus can also be modified through bombardment by high energy subatomic particles or photons. If this modifies the number of protons in a nucleus, the atom changes to a different chemical element.[47][48]

If the mass of the nucleus following a fusion reaction is less than the sum of the masses of the separate particles, then the difference between these two values can be emitted as a type of usable energy (such as a gamma ray, or the kinetic energy of a beta particle), as described by Albert Einstein's mass–energy equivalence formula, E = mc2, where m is the mass loss and c is the speed of light. This deficit is part of the binding energy of the new nucleus, and it is the non-recoverable loss of the energy that causes the fused particles to remain together in a state that requires this energy to separate.[49]

The fusion of two nuclei that create larger nuclei with lower atomic numbers than iron and nickel—a total nucleon number of about 60—is usually an exothermic process that releases more energy than is required to bring them together.[50] It is this energy-releasing process that makes nuclear fusion in stars a self-sustaining reaction. For heavier nuclei, the binding energy per nucleon begins to decrease. That means that a fusion process producing a nucleus that has an atomic number higher than about 26, and a mass number higher than about 60, is an endothermic process. Thus, more massive nuclei cannot undergo an energy-producing fusion reaction that can sustain the hydrostatic equilibrium of a star.[45]

Electron cloud

[edit]
A potential well, showing, according to classical mechanics, the minimum energy V(x) needed to reach each position x. Classically, a particle with energy E is constrained to a range of positions between x1 and x2.

The electrons in an atom are attracted to the protons in the nucleus by the electromagnetic force. This force binds the electrons inside an electrostatic potential well surrounding the smaller nucleus, which means that an external source of energy is needed for the electron to escape. The closer an electron is to the nucleus, the greater the attractive force. Hence electrons bound near the center of the potential well require more energy to escape than those at greater separations.

Electrons, like other particles, have properties of both a particle and a wave. The electron cloud is a region inside the potential well where each electron forms a type of three-dimensional standing wave—a wave form that does not move relative to the nucleus. This behavior is defined by an atomic orbital, a mathematical function that characterises the probability that an electron appears to be at a particular location when its position is measured.[51] Only a discrete (or quantized) set of these orbitals exist around the nucleus, as other possible wave patterns rapidly decay into a more stable form.[52] Orbitals can have one or more ring or node structures, and differ from each other in size, shape and orientation.[53]

3D views of some hydrogen-like atomic orbitals showing probability density and phase (g orbitals and higher are not shown)

Each atomic orbital corresponds to a particular energy level of the electron. The electron can change its state to a higher energy level by absorbing a photon with sufficient energy to boost it into the new quantum state. Likewise, through spontaneous emission, an electron in a higher energy state can drop to a lower energy state while radiating the excess energy as a photon. These characteristic energy values, defined by the differences in the energies of the quantum states, are responsible for atomic spectral lines.[52]

The amount of energy needed to remove or add an electron—the electron binding energy—is far less than the binding energy of nucleons. For example, it requires only 13.6 eV to strip a ground-state electron from a hydrogen atom,[54] compared to 2.23 million eV for splitting a deuterium nucleus.[55] Atoms are electrically neutral if they have an equal number of protons and electrons. Atoms that have either a deficit or a surplus of electrons are called ions. Electrons that are farthest from the nucleus may be transferred to other nearby atoms or shared between atoms. By this mechanism, atoms are able to bond into molecules and other types of chemical compounds like ionic and covalent network crystals.[56]

Properties

[edit]

Nuclear properties

[edit]

By definition, any two atoms with an identical number of protons in their nuclei belong to the same chemical element. Atoms with equal numbers of protons but a different number of neutrons are different isotopes of the same element. For example, all hydrogen atoms admit exactly one proton, but isotopes exist with no neutrons (hydrogen-1, by far the most common form,[57] also called protium), one neutron (deuterium), two neutrons (tritium) and more than two neutrons. The known elements form a set of atomic numbers, from the single-proton element hydrogen up to the 118-proton element oganesson.[58] All known isotopes of elements with atomic numbers greater than 82 are radioactive, although the radioactivity of element 83 (bismuth) is so slight as to be practically negligible.[59][60]

About 339 nuclides occur naturally on Earth,[61] of which 251 (about 74%) have not been observed to decay, and are referred to as "stable isotopes". Only 90 nuclides are stable theoretically, while another 161 (bringing the total to 251) have not been observed to decay, even though in theory it is energetically possible. These are also formally classified as "stable". An additional 35 radioactive nuclides have half-lives longer than 100 million years, and are long-lived enough to have been present since the birth of the Solar System. This collection of 286 nuclides are known as primordial nuclides. Finally, an additional 53 short-lived nuclides are known to occur naturally, as daughter products of primordial nuclide decay (such as radium from uranium), or as products of natural energetic processes on Earth, such as cosmic ray bombardment (for example, carbon-14).[62][note 1]

For 80 of the chemical elements, at least one stable isotope exists. As a rule, there is only a handful of stable isotopes for each of these elements, the average being 3.1 stable isotopes per element. Twenty-six "monoisotopic elements" have only a single stable isotope, while the largest number of stable isotopes observed for any element is ten, for the element tin. Elements 43, 61, and all elements numbered 83 or higher have no stable isotopes.[63]: 1–12 

Stability of isotopes is affected by the ratio of protons to neutrons, and also by the presence of certain "magic numbers" of neutrons or protons that represent closed and filled quantum shells. These quantum shells correspond to a set of energy levels within the shell model of the nucleus; filled shells, such as the filled shell of 50 protons for tin, confers unusual stability on the nuclide. Of the 251 known stable nuclides, only four have both an odd number of protons and odd number of neutrons: hydrogen-2 (deuterium), lithium-6, boron-10, and nitrogen-14. (Tantalum-180m is odd-odd and observationally stable, but is predicted to decay with a very long half-life.) Also, only four naturally occurring, radioactive odd-odd nuclides have a half-life over a billion years: potassium-40, vanadium-50, lanthanum-138, and lutetium-176. Most odd-odd nuclei are highly unstable with respect to beta decay, because the decay products are even-even, and are therefore more strongly bound, due to nuclear pairing effects.[64]

Mass

[edit]

The large majority of an atom's mass comes from the protons and neutrons that make it up. The total number of these particles (called "nucleons") in a given atom is called the mass number. It is a positive integer and dimensionless (instead of having dimension of mass), because it expresses a count. An example of use of a mass number is "carbon-12," which has 12 nucleons (six protons and six neutrons).

The actual mass of an atom at rest is often expressed in daltons (Da), also called the unified atomic mass unit (u). This unit is defined as a twelfth of the mass of a free neutral atom of carbon-12, which is approximately 1.66×10−27 kg.[65] Hydrogen-1 (the lightest isotope of hydrogen which is also the nuclide with the lowest mass) has an atomic weight of 1.007825 Da.[66] The value of this number is called the atomic mass. A given atom has an atomic mass approximately equal (within 1%) to its mass number times the dalton (for example the mass of a nitrogen-14 is roughly 14 Da), but this number will not be exactly an integer except (by definition) in the case of carbon-12.[67] The heaviest stable atom is lead-208,[59] with a mass of 207.9766521 Da.[68]

As even the most massive atoms are far too light to work with directly, chemists instead use the unit of moles. One mole of atoms of any element always has the same number of atoms (about 6.022×1023). This number was chosen so that if an element has an atomic mass of 1 u, a mole of atoms of that element has a mass close to one gram. Because of the definition of the dalton, each carbon-12 atom has an atomic mass of exactly 12 Da, and so a mole of carbon-12 atoms weighs exactly 0.012 kg.[65]

Shape and size

[edit]

Atoms lack a well-defined outer boundary, so their dimensions are usually described in terms of an atomic radius. This is a measure of the distance out to which the electron cloud extends from the nucleus.[69] This assumes the atom to exhibit a spherical shape, which is only obeyed for atoms in vacuum or free space. Atomic radii may be derived from the distances between two nuclei when the two atoms are joined in a chemical bond. The radius varies with the location of an atom on the atomic chart, the type of chemical bond, the number of neighboring atoms (coordination number) and a quantum mechanical property known as spin.[70] On the periodic table of the elements, atom size tends to increase when moving down columns, but decrease when moving across rows (left to right).[71] Consequently, the smallest atom is helium with a radius of 32 pm, while one of the largest is caesium at 225 pm.[72]

When subjected to external forces, like electrical fields, the shape of an atom may deviate from spherical symmetry. The deformation depends on the field magnitude and the orbital type of outer shell electrons, as shown by group-theoretical considerations. Aspherical deviations might be elicited for instance in crystals, where large crystal-electrical fields may occur at low-symmetry lattice sites.[73][74] Significant ellipsoidal deformations have been shown to occur for sulfur ions[75] and chalcogen ions[76] in pyrite-type compounds.

Atomic dimensions are thousands of times smaller than the wavelengths of light (400–700 nm) so they cannot be viewed using an optical microscope, although individual atoms can be observed using a scanning tunneling microscope. To visualize the minuteness of the atom, consider that a typical human hair is about 1 million carbon atoms in width.[77] A single drop of water contains about 2 sextillion (2×1021) atoms of oxygen, and twice the number of hydrogen atoms.[78] A single carat diamond with a mass of 2×10−4 kg contains about 10 sextillion (1022) atoms of carbon.[note 2] If an apple were magnified to the size of the Earth, then the atoms in the apple would be approximately the size of the original apple.[79]

Radioactive decay

[edit]
This diagram shows the half-life (T12) of various isotopes with Z protons and N neutrons.

Every element has one or more isotopes that have unstable nuclei that are subject to radioactive decay, causing the nucleus to emit particles or electromagnetic radiation. Radioactivity can occur when the radius of a nucleus is large compared with the radius of the strong force, which only acts over distances on the order of 1 fm.[80]

The most common forms of radioactive decay are:[81][82]

  • Alpha decay: this process is caused when the nucleus emits an alpha particle, which is a helium nucleus consisting of two protons and two neutrons. The result of the emission is a new element with a lower atomic number.
  • Beta decay (and electron capture): these processes are regulated by the weak force, and result from a transformation of a neutron into a proton, or a proton into a neutron. The neutron to proton transition is accompanied by the emission of an electron and an antineutrino, while proton to neutron transition (except in electron capture) causes the emission of a positron and a neutrino. The electron or positron emissions are called beta particles. Beta decay either increases or decreases the atomic number of the nucleus by one. Electron capture is more common than positron emission, because it requires less energy. In this type of decay, an electron is absorbed by the nucleus, rather than a positron emitted from the nucleus. A neutrino is still emitted in this process, and a proton changes to a neutron.
  • Gamma decay: this process results from a change in the energy level of the nucleus to a lower state, resulting in the emission of electromagnetic radiation. The excited state of a nucleus which results in gamma emission usually occurs following the emission of an alpha or a beta particle. Thus, gamma decay usually follows alpha or beta decay.

Other more rare types of radioactive decay include ejection of neutrons or protons or clusters of nucleons from a nucleus, or more than one beta particle. An analog of gamma emission which allows excited nuclei to lose energy in a different way, is internal conversion—a process that produces high-speed electrons that are not beta rays, followed by production of high-energy photons that are not gamma rays. A few large nuclei explode into two or more charged fragments of varying masses plus several neutrons, in a decay called spontaneous nuclear fission.

Each radioactive isotope has a characteristic decay time period—the half-life—that is determined by the amount of time needed for half of a sample to decay. This is an exponential decay process that steadily decreases the proportion of the remaining isotope by 50% every half-life. Hence after two half-lives have passed only 25% of the isotope is present, and so forth.[80]

Magnetic moment

[edit]

Elementary particles possess an intrinsic quantum mechanical property known as spin. This is analogous to the angular momentum of an object that is spinning around its center of mass, although strictly speaking these particles are believed to be point-like and cannot be said to be rotating. Spin is measured in units of the reduced Planck constant (ħ), with electrons, protons and neutrons all having spin 12 ħ, or "spin-12". In an atom, electrons in motion around the nucleus possess orbital angular momentum in addition to their spin, while the nucleus itself possesses angular momentum due to its nuclear spin.[83]

The magnetic field produced by an atom—its magnetic moment—is determined by these various forms of angular momentum, just as a rotating charged object classically produces a magnetic field, but the most dominant contribution comes from electron spin. Due to the nature of electrons to obey the Pauli exclusion principle, in which no two electrons may be found in the same quantum state, bound electrons pair up with each other, with one member of each pair in a spin up state and the other in the opposite, spin down state. Thus these spins cancel each other out, reducing the total magnetic dipole moment to zero in some atoms with even number of electrons.[84]

In ferromagnetic elements such as iron, cobalt and nickel, an odd number of electrons leads to an unpaired electron and a net overall magnetic moment. The orbitals of neighboring atoms overlap and a lower energy state is achieved when the spins of unpaired electrons are aligned with each other, a spontaneous process known as an exchange interaction. When the magnetic moments of ferromagnetic atoms are lined up, the material can produce a measurable macroscopic field. Paramagnetic materials have atoms with magnetic moments that line up in random directions when no magnetic field is present, but the magnetic moments of the individual atoms line up in the presence of a field.[84][85]

The nucleus of an atom will have no spin when it has even numbers of both neutrons and protons, but for other cases of odd numbers, the nucleus may have a spin. Normally nuclei with spin are aligned in random directions because of thermal equilibrium, but for certain elements (such as xenon-129) it is possible to polarize a significant proportion of the nuclear spin states so that they are aligned in the same direction—a condition called hyperpolarization. This has important applications in magnetic resonance imaging.[86][87]

Energy levels

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These electron's energy levels (not to scale) are sufficient for ground states of atoms up to cadmium (5s2 4d10) inclusively. The top of the diagram is lower than an unbound electron state.

The potential energy of an electron in an atom is negative relative to when the distance from the nucleus goes to infinity; its dependence on the electron's position reaches the minimum inside the nucleus, roughly in inverse proportion to the distance. In the quantum-mechanical model, a bound electron can occupy only a set of states centered on the nucleus, and each state corresponds to a specific energy level; see time-independent Schrödinger equation for a theoretical explanation. An energy level can be measured by the amount of energy needed to unbind the electron from the atom, and is usually given in units of electronvolts (eV). The lowest energy state of a bound electron is called the ground state, i.e., stationary state, while an electron transition to a higher level results in an excited state.[88] The electron's energy increases along with n because the (average) distance to the nucleus increases. Dependence of the energy on is caused not by the electrostatic potential of the nucleus, but by interaction between electrons.

For an electron to transition between two different states, e.g. ground state to first excited state, it must absorb or emit a photon at an energy matching the difference in the potential energy of those levels, according to the Niels Bohr model, what can be precisely calculated by the Schrödinger equation. Electrons jump between orbitals in a particle-like fashion. For example, if a single photon strikes the electrons, only a single electron changes states in response to the photon; see Electron properties.

The energy of an emitted photon is proportional to its frequency, so these specific energy levels appear as distinct bands in the electromagnetic spectrum.[89] Each element has a characteristic spectrum that can depend on the nuclear charge, subshells filled by electrons, the electromagnetic interactions between the electrons and other factors.[90]

An example of absorption lines in a spectrum

When a continuous spectrum of energy is passed through a gas or plasma, some of the photons are absorbed by atoms, causing electrons to change their energy level. Those excited electrons that remain bound to their atom spontaneously emit this energy as a photon, traveling in a random direction, and so drop back to lower energy levels. Thus the atoms behave like a filter that forms a series of dark absorption bands in the energy output. An observer viewing the atoms from a view that does not include the continuous spectrum in the background, instead sees a series of emission lines from the photons emitted by the atoms. Spectroscopic measurements of the strength and width of atomic spectral lines allow the composition and physical properties of a substance to be determined.[91]

Close examination of the spectral lines reveals that some display a fine structure splitting. This occurs because of spin–orbit coupling, which is an interaction between the spin and motion of the outermost electron.[92] When an atom is in an external magnetic field, spectral lines become split into three or more components; a phenomenon called the Zeeman effect. This is caused by the interaction of the magnetic field with the magnetic moment of the atom and its electrons. Some atoms can have multiple electron configurations with the same energy level, which thus appear as a single spectral line. The interaction of the magnetic field with the atom shifts these electron configurations to slightly different energy levels, resulting in multiple spectral lines.[93] The presence of an external electric field can cause a comparable splitting and shifting of spectral lines by modifying the electron energy levels, a phenomenon called the Stark effect.[94]

If a bound electron is in an excited state, an interacting photon with the proper energy can cause stimulated emission of a photon with a matching energy level. For this to occur, the electron must drop to a lower energy state that has an energy difference matching the energy of the interacting photon. The emitted photon and the interacting photon then move off in parallel and with matching phases. That is, the wave patterns of the two photons are synchronized. This physical property is used to make lasers, which can emit a coherent beam of light energy in a narrow frequency band.[95]

Valence and bonding behavior

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Valency is the combining power of an element. It is determined by the number of bonds it can form to other atoms or groups.[96] The outermost electron shell of an atom in its uncombined state is known as the valence shell, and the electrons in that shell are called valence electrons. The number of valence electrons determines the bonding behavior with other atoms. Atoms tend to chemically react with each other in a manner that fills (or empties) their outer valence shells.[97] For example, a transfer of a single electron between atoms is a useful approximation for bonds that form between atoms with one-electron more than a filled shell, and others that are one-electron short of a full shell, such as occurs in the compound sodium chloride and other chemical ionic salts. Many elements display multiple valences, or tendencies to share differing numbers of electrons in different compounds. Thus, chemical bonding between these elements takes many forms of electron-sharing that are more than simple electron transfers. Examples include the element carbon and the organic compounds.[98]

The chemical elements are often displayed in a periodic table that is laid out to display recurring chemical properties, and elements with the same number of valence electrons form a group that is aligned in the same column of the table. (The horizontal rows correspond to the filling of a quantum shell of electrons.) The elements at the far right of the table have their outer shell completely filled with electrons, which results in chemically inert elements known as the noble gases.[99][100]

States

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Graphic illustrating the formation of a Bose–Einstein condensate

Quantities of atoms are found in different states of matter that depend on the physical conditions, such as temperature and pressure. By varying the conditions, materials can transition between solids, liquids, gases, and plasmas.[101] Within a state, a material can also exist in different allotropes. An example of this is solid carbon, which can exist as graphite or diamond.[102] Gaseous allotropes exist as well, such as dioxygen and ozone.

At temperatures close to absolute zero, atoms can form a Bose–Einstein condensate, at which point quantum mechanical effects, which are normally only observed at the atomic scale, become apparent on a macroscopic scale.[103][104] This super-cooled collection of atoms then behaves as a single super atom, which may allow fundamental checks of quantum mechanical behavior.[105]

Identification

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Scanning tunneling microscope surface reconstruction image showing the individual atoms making up this gold (100) surface. The surface atoms deviate from the bulk crystal structure and arrange in columns several atoms wide with pits between them.

While atoms are too small to be seen, devices such as the scanning tunneling microscope (STM) enable their visualization at the surfaces of solids. The microscope uses the quantum tunneling phenomenon, which allows particles to pass through a barrier that would be insurmountable in the classical perspective. Electrons tunnel through the vacuum between two biased electrodes, providing a tunneling current that is exponentially dependent on their separation. One electrode is a sharp tip ideally ending with a single atom. At each point of the scan of the surface the tip's height is adjusted so as to keep the tunneling current at a set value. How much the tip moves to and away from the surface is interpreted as the height profile. For low bias, the microscope images the averaged electron orbitals across closely packed energy levels—the local density of the electronic states near the Fermi level.[106][107] Because of the distances involved, both electrodes need to be extremely stable; only then periodicities can be observed that correspond to individual atoms. The method alone is not chemically specific, and cannot identify the atomic species present at the surface.

Atoms can be easily identified by their mass. If an atom is ionized by removing one of its electrons, its trajectory when it passes through a magnetic field will bend. The radius by which the trajectory of a moving ion is turned by the magnetic field is determined by the mass of the atom. The mass spectrometer uses this principle to measure the mass-to-charge ratio of ions. If a sample contains multiple isotopes, the mass spectrometer can determine the proportion of each isotope in the sample by measuring the intensity of the different beams of ions. Techniques to vaporize atoms include inductively coupled plasma atomic emission spectroscopy and inductively coupled plasma mass spectrometry, both of which use a plasma to vaporize samples for analysis.[108]

The atom-probe tomograph has sub-nanometer resolution in 3-D and can chemically identify individual atoms using time-of-flight mass spectrometry.[109]

Electron emission techniques such as X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), which measure the binding energies of the core electrons, are used to identify the atomic species present in a sample in a non-destructive way. With proper focusing both can be made area-specific. Another such method is electron energy loss spectroscopy (EELS), which measures the energy loss of an electron beam within a transmission electron microscope when it interacts with a portion of a sample.

Spectra of excited states can be used to analyze the atomic composition of distant stars. Specific light wavelengths contained in the observed light from stars can be separated out and related to the quantized transitions in free gas atoms. These colors can be replicated using a gas-discharge lamp containing the same element.[110] Helium was discovered in this way in the spectrum of the Sun 23 years before it was found on Earth.[111]

Origin and current state

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Baryonic matter forms about 4% of the total energy density of the observable universe, with an average density of about 0.25 particles/m3 (mostly protons and electrons).[112] Within a galaxy such as the Milky Way, particles have a much higher concentration, with the density of matter in the interstellar medium (ISM) ranging from 105 to 109 atoms/m3.[113] The Sun is believed to be inside the Local Bubble, so the density in the solar neighborhood is only about 103 atoms/m3.[114] Stars form from dense clouds in the ISM, and the evolutionary processes of stars result in the steady enrichment of the ISM with elements more massive than hydrogen and helium.

Up to 95% of the Milky Way's baryonic matter are concentrated inside stars, where conditions are unfavorable for atomic matter. The total baryonic mass is about 10% of the mass of the galaxy;[115] the remainder of the mass is an unknown dark matter.[116] High temperature inside stars makes most "atoms" fully ionized, that is, separates all electrons from the nuclei. In stellar remnants—with exception of their surface layers—an immense pressure make electron shells impossible.

Formation

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Periodic table showing the origin of each element. Elements from carbon up to sulfur may be made in small stars by the alpha process. Elements beyond iron are made in large stars with slow neutron capture (s-process). Elements heavier than iron may be made in neutron star mergers or supernovae after the r-process.

Electrons are thought to exist in the Universe since early stages of the Big Bang. Atomic nuclei forms in nucleosynthesis reactions. In about three minutes Big Bang nucleosynthesis produced most of the helium, lithium, and deuterium in the Universe, and perhaps some of the beryllium and boron.[117][118][119]

Ubiquitousness and stability of atoms relies on their binding energy, which means that an atom has a lower energy than an unbound system of the nucleus and electrons. Where the temperature is much higher than ionization potential, the matter exists in the form of plasma—a gas of positively charged ions (possibly, bare nuclei) and electrons. When the temperature drops below the ionization potential, atoms become statistically favorable. Atoms (complete with bound electrons) became to dominate over charged particles 380,000 years after the Big Bang—an epoch called recombination, when the expanding Universe cooled enough to allow electrons to become attached to nuclei.[120]

Since the Big Bang, which produced no carbon or heavier elements, atomic nuclei have been combined in stars through the process of nuclear fusion to produce more of the element helium, and (via the triple-alpha process) the sequence of elements from carbon up to iron;[121] see stellar nucleosynthesis for details.

Isotopes such as lithium-6, as well as some beryllium and boron are generated in space through cosmic ray spallation.[122] This occurs when a high-energy proton strikes an atomic nucleus, causing large numbers of nucleons to be ejected.

Elements heavier than iron were produced in supernovae and colliding neutron stars through the r-process, and in AGB stars through the s-process, both of which involve the capture of neutrons by atomic nuclei.[123] Elements such as lead formed largely through the radioactive decay of heavier elements.[124]

Earth

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Most of the atoms that make up the Earth and its inhabitants were present in their current form in the nebula that collapsed out of a molecular cloud to form the Solar System. The rest are the result of radioactive decay, and their relative proportion can be used to determine the age of the Earth through radiometric dating.[125][126] Most of the helium in the crust of the Earth (about 99% of the helium from gas wells, as shown by its lower abundance of helium-3) is a product of alpha decay.[127]

There are a few trace atoms on Earth that were not present at the beginning (i.e., not "primordial"), nor are results of radioactive decay. Carbon-14 is continuously generated by cosmic rays in the atmosphere.[128] Some atoms on Earth have been artificially generated either deliberately or as by-products of nuclear reactors or explosions.[129][130] Of the transuranic elements—those with atomic numbers greater than 92—only plutonium and neptunium occur naturally on Earth.[131][132] Transuranic elements have radioactive lifetimes shorter than the current age of the Earth[133] and thus identifiable quantities of these elements have long since decayed, with the exception of traces of plutonium-244 possibly deposited by cosmic dust.[125] Natural deposits of plutonium and neptunium are produced by neutron capture in uranium ore.[134]

The Earth contains approximately 1.33×1050 atoms.[135] Although small numbers of independent atoms of noble gases exist, such as argon, neon, and helium, 99% of the atmosphere is bound in the form of molecules, including carbon dioxide and diatomic oxygen and nitrogen. At the surface of the Earth, an overwhelming majority of atoms combine to form various compounds, including water, salt, silicates, and oxides. Atoms can also combine to create materials that do not consist of discrete molecules, including crystals and liquid or solid metals.[136][137] This atomic matter forms networked arrangements that lack the particular type of small-scale interrupted order associated with molecular matter.[138]

Rare and theoretical forms

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Superheavy elements

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All nuclides with atomic numbers higher than 82 (lead) are known to be radioactive. No nuclide with an atomic number exceeding 92 (uranium) exists on Earth as a primordial nuclide, and heavier elements generally have shorter half-lives. Nevertheless, an "island of stability" encompassing relatively long-lived isotopes of superheavy elements[139] with atomic numbers 110 to 114 might exist.[140] Predictions for the half-life of the most stable nuclide on the island range from a few minutes to millions of years.[141] In any case, superheavy elements (with Z > 104) would not exist due to increasing Coulomb repulsion (which results in spontaneous fission with increasingly short half-lives) in the absence of any stabilizing effects.[142]

Exotic matter

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Each particle of matter has a corresponding antimatter particle with the opposite electrical charge. Thus, the positron is a positively charged antielectron and the antiproton is a negatively charged equivalent of a proton. When a matter and corresponding antimatter particle meet, they annihilate each other. Because of this, along with an imbalance between the number of matter and antimatter particles, the latter are rare in the universe. The first causes of this imbalance are not yet fully understood, although theories of baryogenesis may offer an explanation. As a result, no antimatter atoms have been discovered in nature.[143][144] In 1996, the antimatter counterpart of the hydrogen atom (antihydrogen) was synthesized at the CERN laboratory in Geneva.[145][146]

Other exotic atoms have been created by replacing one of the protons, neutrons or electrons with other particles that have the same charge. For example, an electron can be replaced by a more massive muon, forming a muonic atom. These types of atoms can be used to test fundamental predictions of physics.[147][148][149]

See also

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Notes

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References

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Bibliography

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Further reading

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Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
An atom is the fundamental unit of matter that retains the chemical properties of an element, consisting of a central nucleus composed of positively charged protons and uncharged neutrons, surrounded by a cloud of negatively charged electrons. The number of protons in the nucleus, known as the , uniquely identifies the element, while the total number of protons and neutrons defines the atom's . Electrons, which are much lighter than protons or neutrons, occupy probabilistic orbitals around the nucleus, enabling atoms to form bonds and molecules through electron interactions. The concept of the atom originated in ancient Greek philosophy, with philosopher around 440 BCE proposing that matter consists of indivisible particles called atomos, meaning "uncuttable" in Greek. Modern atomic theory was established in the early 19th century by , who described atoms as indestructible spheres combining in fixed ratios to form compounds. Key experimental discoveries followed: in 1897, J.J. Thomson identified the as a ; in 1911 revealed the nuclear structure through gold foil experiments; and discovered the neutron in 1932. These advancements confirmed that atoms are not truly indivisible but are composed of smaller particles, with protons and neutrons themselves made of fundamental quarks. Atoms form the basis of all ordinary matter in the , originating from the primordial following the approximately 13.8 billion years ago, when light elements like and were first produced. Variations in count create isotopes, some of which are stable and others radioactive, influencing nuclear processes like fission and fusion that power stars and . The diameter of an atom typically ranges from 0.1 to 0.5 nanometers, with the cloud extending vastly larger—up to 10,000 times the nucleus size—yet the nucleus holds over 99.9% of the atom's mass. Understanding atomic structure underpins fields from chemistry and to and .

Historical Development

Philosophical Foundations

The concept of the atom originated in during the 5th century BCE, where and his student proposed that all matter consists of indivisible, eternal particles called atomos, meaning "uncuttable" or "indivisible," moving through to form the visible world through their combinations and interactions. These atomists argued that atomos were solid, impenetrable, and varied in shape, size, and position, providing a mechanistic explanation for change and diversity in nature without invoking divine intervention or . Parallel ideas emerged independently in ancient , particularly within the Nyāya-Vaiśeṣika school, which posited paramāṇu as the ultimate, indivisible units of matter that combine to form composite substances and explain the creation and dissolution of the physical world. In texts like the Vaiśeṣika Sūtra (circa 2nd century BCE to 1st century CE), paramāṇu were described as eternal, partless particles possessing inherent qualities such as motion and combining under unseen forces to manifest grosser forms of matter. This atomistic framework integrated with broader metaphysical categories, emphasizing qualities, actions, and universals as fundamental realities alongside these minimal material units. Aristotle vehemently opposed this atomistic view in the 4th century BCE, advocating instead for matter as continuous and infinitely divisible, arguing that discrete particles would imply voids, which he deemed impossible since nature abhors a . His hylomorphic theory, positing matter as a substrate informed by form and actualized through potentiality, dominated Western thought and suppressed during the medieval period, where scholastic philosophers largely favored continuous substance over discrete particles. The philosophical foundations of atomism experienced a revival in the through , who reformulated Epicurean ideas into a Christian-compatible corpuscular , describing atoms as tiny, solid, indivisible bodies created by and endowed with motion to account for natural phenomena. 's Syntagma Philosophicum (published posthumously in 1658) emphasized sensory evidence and mechanistic principles, bridging ancient with emerging scientific inquiry. further advanced these ideas in the 1704 edition of , where in a series of queries, he speculated on atoms as hard, impenetrable, movable particles whose attractions and repulsions underpin chemical affinities and the cohesion of bodies, laying conceptual groundwork for later empirical developments.

Classical Atomic Theory

The classical atomic theory emerged in the early as chemists sought empirical explanations for the patterns observed in chemical reactions, shifting from philosophical speculation to quantitative evidence. formulated the in 1803, observing that when two elements form more than one , the masses of one element that combine with a fixed mass of the other are in the ratios of small whole numbers, such as the 1:2 of oxygen in (CO) and (CO₂). This law provided key support for the existence of atoms as discrete units of matter. In 1808, Dalton fully articulated his atomic theory in A New System of Chemical Philosophy, proposing that all matter consists of tiny, indivisible particles called atoms; atoms of the same element are identical in mass and properties, while atoms of different elements differ; atoms combine in simple whole-number ratios to form compounds; and atoms are indestructible and indivisible by chemical means. These postulates explained the and multiple proportions, establishing atoms as the fundamental building blocks of chemical substances. Avogadro's hypothesis, proposed in 1811, advanced this framework by stating that equal volumes of all gases, at the same temperature and pressure, contain equal numbers of molecules, allowing chemists to differentiate between atomic and molecular forms of elements and to calculate relative atomic weights more accurately. This idea resolved inconsistencies in Dalton's assignments of atomic weights and facilitated the quantitative study of gases. Building on these foundations, early attempts to organize elements by atomic weights revealed periodic patterns. In 1829, identified triads of elements with similar chemical properties, where the atomic weight of the middle element was approximately the average of the other two, such as (35.5), (80), and iodine (127). Later, in 1865, John Newlands arranged known elements in order of increasing atomic weight and noted that their properties repeated every eighth element, akin to the octaves in music, though his scheme was limited by incomplete atomic weight data. These precursors laid the groundwork for the modern periodic table.

Key Experimental Discoveries

In 1897, J.J. Thomson conducted experiments using cathode ray tubes, where streams of particles emitted from the cathode were deflected by electric and magnetic fields, revealing that these rays consisted of negatively charged particles much smaller than atoms. By measuring the deflection, Thomson calculated the charge-to-mass ratio e/me/m of these particles to be approximately 1.76×10111.76 \times 10^{11} C/kg, establishing the existence of the as a fundamental component of matter. To determine the electron's absolute charge, Robert Millikan performed the starting in 1909, ionizing oil droplets and balancing their gravitational fall against electrostatic forces in a controlled . This yielded the e=1.602×1019e = 1.602 \times 10^{-19} C, confirming that is quantized in discrete units. Ernest Rutherford's 1911 foil experiment further probed atomic structure by directing s at a thin sheet of foil and observing their patterns on a fluorescent screen. While most particles passed through undeflected, a small fraction scattered at large angles, indicating that the atom's positive charge and mass were concentrated in a tiny, dense nucleus rather than diffusely distributed. Rutherford derived a formula for the differential cross-section, dσdΩ=(Z1Z2e28πϵ0E)21sin4(θ/2),\frac{d\sigma}{d\Omega} = \left( \frac{Z_1 Z_2 e^2}{8\pi \epsilon_0 E} \right)^2 \frac{1}{\sin^4(\theta/2)}, where Z1Z_1 and Z2Z_2 are the atomic numbers of the incident and target particles, ee is the , ϵ0\epsilon_0 is the , and EE is the of the , which quantitatively matched the observed distribution. Between 1917 and 1919, Rutherford extended his scattering studies by bombarding light elements like with alpha particles, detecting nuclei ejected from the targets, which he identified as positively charged protons constituting the nucleus of the . These experiments demonstrated that protons were fundamental building blocks present in all atomic nuclei. In 1932, irradiated with alpha particles, producing highly penetrating neutral radiation that knocked protons out of with energies inconsistent with gamma rays. Analyzing the momentum transfer, Chadwick concluded these were neutrons—uncharged particles with mass nearly equal to the proton—resolving discrepancies in atomic masses and explaining the existence of isotopes with the same but different masses.

Quantum Mechanical Model

The quantum mechanical model of the atom represents a from classical descriptions, incorporating the wave-particle duality of electrons, where they exhibit both particle-like and wave-like properties, leading to probabilistic interpretations of their positions rather than definite orbits. This framework emerged in the early to resolve inconsistencies in , such as the stability of atoms and the discrete nature of atomic spectra, by treating electrons as solutions to wave equations that yield probability distributions for their locations. A foundational step was Niels Bohr's 1913 model, which introduced quantized for the in , given by L=nL = n \hbar, where nn is a positive integer (the principal ) and =h/2π\hbar = h / 2\pi is the reduced Planck's constant. This quantization condition, combined with balancing centripetal and forces, yielded discrete energy levels En=13.6eVn2E_n = -\frac{13.6 \, \text{eV}}{n^2} for the , accurately predicting its . Although semi-classical, Bohr's model laid the groundwork for full quantum treatments by imposing discreteness on continuous classical motion. The complete quantum description arrived with Erwin Schrödinger's 1926 wave equation, a governing the electron's ψ(r,θ,ϕ)\psi(r, \theta, \phi) in spherical coordinates for the : 22m2ψe24πϵ0rψ=Eψ,-\frac{\hbar^2}{2m} \nabla^2 \psi - \frac{e^2}{4\pi \epsilon_0 r} \psi = E \psi, where mm and ee are the and charge, respectively, and 2\nabla^2 is the Laplacian operator. Solutions to this time-independent equation separate into radial and angular parts, producing hydrogen-like atomic orbitals characterized by quantum numbers nn, ll (azimuthal), and mlm_l (magnetic), with ψ2|\psi|^2 giving the probability density for finding the ./11%3A_Quantum_Mechanics_and_Atomic_Structure/11.10%3A_The_Schrodinger_Wave_Equation_for_the_Hydrogen_Atom) These orbitals replace Bohr's circular orbits with three-dimensional probability clouds, explaining atomic stability through interference. For multi-electron atoms, the , formulated by in 1925, states that no two electrons can occupy the same simultaneously, ensuring distinct orbitals for each electron. This principle, initially proposed to explain in atomic spectra, relies on electrons possessing an intrinsic or spin. In 1925, and introduced electron spin as a fourth s=±1/2s = \pm 1/2, attributing the anomalous to this , with spin S=2σ\mathbf{S} = \frac{\hbar}{2} \boldsymbol{\sigma} (where σ\boldsymbol{\sigma} are ). Combining spin with orbital quantum numbers, the exclusion principle limits each orbital to at most two electrons of opposite spin. The Heisenberg uncertainty principle, articulated by in 1927, further underscores the probabilistic nature of the quantum atom: ΔxΔp2\Delta x \Delta p \geq \frac{\hbar}{2}, where Δx\Delta x and Δp\Delta p are uncertainties in position and . This implies that precise knowledge of an electron's position precludes exact momentum determination, rendering classical trajectories impossible and confining electrons to delocalized orbitals with inherent spread, which stabilizes atoms against radiation. To approximate solutions for multi-electron atoms, where the becomes intractable due to electron-electron interactions, the Hartree-Fock method employs a mean-field approach. Developed by in 1928 and refined by in 1930, it assumes each moves in an effective potential from the nucleus and the averaged charge distribution of other electrons, yielding self-consistent single-particle orbitals via iterative solution of coupled equations. This approximation captures much of the electronic structure, though it neglects instantaneous correlations between electrons.

Atomic Structure

The atomic structure describes the organization of an atom's subatomic components, featuring a central, positively charged nucleus composed of protons and neutrons, which accounts for nearly all of the atom's mass, surrounded by a probabilistic cloud of negatively charged electrons. This configuration, established through early 20th-century experiments and quantum mechanics, determines the atom's chemical and physical properties.

Subatomic Particles

Atoms are composed of three primary types of subatomic particles: protons, neutrons, and , which together determine the atom's fundamental properties such as and mass. These particles are the building blocks that form the nucleus and surrounding electron cloud, with protons and neutrons residing in the dense central nucleus and electrons occupying the outer regions. Protons carry a positive of +e+e, where ee is the with a value of 1.602176634×10191.602176634 \times 10^{-19} C, and have a rest mass of approximately 1.6726×10271.6726 \times 10^{-27} kg. The number of protons in an atom's nucleus, denoted by the ZZ, uniquely identifies the and governs its chemical behavior. Neutrons are electrically neutral particles with no net charge and a rest mass of approximately 1.6749×10271.6749 \times 10^{-27} kg, slightly greater than that of the proton. They contribute to the atom's without affecting its charge; the total number of protons and neutrons, known as the AA, approximates the in atomic mass units. Electrons possess a negative charge of e-e and have a much smaller rest mass of approximately 9.109×10319.109 \times 10^{-31} kg, which is about 1/[1836](/page/1836)1/[1836](/page/1836) that of a proton, rendering their contribution to the atom's total negligible. Despite their light weight, electrons play a crucial role in atomic interactions and chemical bonding due to their position outside the nucleus. At a deeper level, protons and neutrons are not elementary but composite particles made of quarks bound by the mediated by gluons. A proton consists of two s and one (uud), while a neutron comprises one and two s (udd); electrons, however, are fundamental leptons with no known substructure. In the context of atoms, protons and neutrons function as effective units, as quarks are confined within hadrons and not observed in isolation. Antimatter counterparts of these particles exist in exotic contexts, such as particle accelerators or cosmic rays, including the (antielectron) with charge +e+e and mass identical to the , the with charge e-e and content uˉuˉdˉ\bar{u}\bar{u}\bar{d}, and the with neutral charge and uˉdˉdˉ\bar{u}\bar{d}\bar{d} composition. These antiparticles annihilate upon contact with their counterparts, releasing , but play no in ordinary atomic .

Nuclear Composition

The constitutes the central core of an atom, with a on the order of 101510^{-15} (1 femtometer), containing ZZ protons and N=AZN = A - Z neutrons, where AA is the representing the total number of nucleons. This compact structure, vastly smaller than the surrounding cloud, holds over 99.9% of the atom's due to the close packing of these subatomic particles. The protons and neutrons, collectively known as nucleons, are bound together by the strong nuclear force, a that acts over extremely short distances of approximately 1 femtometer. This force originates from the underlying mediated by gluons between quarks within the nucleons, resulting in a residual attraction that overcomes the electromagnetic repulsion between the positively charged protons. Without this overpowering attraction, the electrostatic repulsion would cause the nucleus to disintegrate, highlighting the strong force's essential role in maintaining nuclear stability. The stability of the nucleus arises from its , defined as the energy required to disassemble it into its individual protons and s. This energy is calculated using the mass-energy equivalence principle: Eb=[Zmp+NmnM]c2E_b = \left[ Z m_p + N m_n - M \right] c^2 where mpm_p and mnm_n are the masses of the proton and , respectively, MM is the measured of the nucleus, and cc is the . The difference Zmp+NmnMZ m_p + N m_n - M, known as the mass defect, reflects the conversion of into binding energy during nucleus formation. To approximate this binding energy across different nuclei, the , developed by and , incorporates terms for volume, surface, repulsion, asymmetry, and pairing effects, providing a macroscopic description of nuclear es. Isotopes are variants of an element with the same ZZ (and thus the same number of protons) but different numbers of neutrons NN, leading to distinct mass numbers AA. For instance, (12C^{12}\mathrm{C}, with 6 protons and 6 neutrons) and (14C^{14}\mathrm{C}, with 6 protons and 8 neutrons) are , differing in nuclear stability and applications such as dating in . Two primary theoretical models describe the nucleus's composition and behavior: the liquid drop model and the . The liquid drop model, analogous to a charged incompressible fluid, treats the nucleus as a droplet where nucleons interact collectively, accounting for bulk properties like through and electrostatic terms; it was notably applied by to explain . In contrast, the views nucleons as occupying discrete energy levels or "shells" governed by , similar to electrons in atoms, with strong spin-orbit coupling explaining periodic variations in nuclear properties such as magic numbers (e.g., 2, 8, 20, 28); this model was independently developed by and J. Hans D. Jensen. These models complement each other, with the liquid drop providing a global view and the capturing microscopic details.

Electron Arrangement

Electrons in an atom occupy specific regions of space around the nucleus known as atomic orbitals, which are solutions to the describing the probability distribution of positions. These orbitals are organized into shells and subshells based on quantum mechanical principles, providing the framework for the atom's electronic structure. The arrangement of is specified by four . The principal quantum number nn determines the and average distance from the nucleus, taking positive integer values (n=1,2,3,n = 1, 2, 3, \ldots). The ll, also called the quantum number, defines the subshell and orbital shape, ranging from 0 to n1n-1 (with l=0l = 0 for s, 1 for p, 2 for d, and 3 for f orbitals). The mlm_l specifies the orbital's orientation in space, ranging from l-l to +l+l in integer steps. The msm_s describes the 's intrinsic spin, with values of +12+\frac{1}{2} or 12-\frac{1}{2}. These quantum numbers ensure that no two in an atom share the same set, as per the . Atomic orbitals have characteristic shapes determined by the ll. S orbitals (l=0l = 0) are spherical, symmetric around the nucleus. P orbitals (l=1l = 1) have a dumbbell shape with two lobes along one axis (x, y, or z). D orbitals (l=2l = 2) exhibit more complex cloverleaf or double- shapes, while f orbitals (l=3l = 3) are even more intricate with multiple lobes. The electron's location is probabilistic, given by the square of the wave function ψ2|\psi|^2, which represents the probability density of finding the at a particular point in space. Electrons fill orbitals according to the , which states that orbitals are occupied in order of increasing energy, starting with the lowest available. The typical filling sequence is 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, and so on, accommodating up to 2 electrons per orbital. Hund's rule governs the arrangement within degenerate orbitals (those of equal energy), requiring electrons to occupy separate orbitals with parallel spins before pairing up, thereby maximizing the total spin angular momentum. This filling pattern results in ground-state electron configurations that correlate directly with the periodic table's block structure. The s-block elements (groups 1 and 2) have valence electrons in ns orbitals, typically ns¹ or ns² configurations. The p-block elements (groups 13–18) fill np orbitals, leading to ns²np¹ through ns²np⁶ valence setups. In heavy atoms, relativistic effects become significant due to high nuclear charge, causing inner s to move at speeds approaching the . This leads to relativistic contraction of s and p orbitals, stabilizing them relative to d and f orbitals and altering electron configurations. For example, in (atomic number 79), these effects narrow the energy gap between 5d and 6s orbitals, shifting absorption of blue light and resulting in the metal's characteristic yellow color.

Physical Properties

Mass and Charge

The mass of an atom is predominantly contributed by its nucleus, where protons and neutrons account for nearly all of the total , as the mass of s is negligible—approximately 1/1836 that of a proton. es are conventionally expressed in unified atomic mass units (u), defined such that 1 u equals one-twelfth the of a atom at rest in its , corresponding to 1.660539 × 10^{-27} kg. For instance, the protium isotope (hydrogen-1) has an atomic of approximately 1.0078 u, reflecting the slight excess over the proton's due to the and electron contribution. While isotopic masses refer to the specific mass of a single , the for an element is a weighted based on its isotopic abundances. This distinction is evident in elements like , where the atomic weight of 35.45 u arises from the prevalence of chlorine-35 (about 75.8%) and chlorine-37 (about 24.2%), rather than an exact integer value. Such weighted averages are crucial for chemical calculations, as they represent the effective mass encountered in typical samples. A neutral atom possesses zero net charge due to the exact balance between the positive charges of its Z protons in the nucleus and the negative charges of its Z electrons orbiting the nucleus. disrupts this neutrality: loss of one or more electrons produces a cation with a net positive charge, while gain of electrons yields an anion with a net negative charge. Precise measurement of atomic and isotopic masses relies on , a technique developed by Francis Aston in 1919 using his mass spectrograph to ionize atoms and separate them by . Aston's work revealed the "whole number rule," showing that isotopic masses are very close to integer multiples of the hydrogen mass but deviate slightly due to nuclear binding effects, enabling the discovery of non-radiogenic isotopes and refining scales.

Size and Shape

The size of an atom is typically on the order of 101010^{-10} meters, or 1 angstrom (Å), representing the scale at which atomic dimensions are measured. This scale encompasses different measures of atomic radius depending on the context: the covalent radius is half the distance between nuclei of two identical atoms sharing a bond, the van der Waals radius is half the distance between non-bonded atoms in close contact, and the ionic radius applies to atoms in ionic compounds where size varies with charge. These variants highlight how atomic size adapts to bonding environments, with covalent radii generally smaller than van der Waals radii due to orbital overlap. In the quantum mechanical description, the spatial extent of an atom is defined by the electron cloud rather than a fixed boundary. For the hydrogen atom in its ground state, the Bohr radius a0=5.29×1011a_0 = 5.29 \times 10^{-11} m serves as a fundamental unit, representing the most probable distance of the electron from the nucleus. For hydrogen-like atoms, the electron cloud's extent scales with the square of the principal quantum number nn, such that approximately 99% of the electron probability density is contained within a radius on the order of n2a0n^2 a_0. This probabilistic distribution arises from the wave nature of electrons, where electron orbitals define regions of high probability rather than precise paths. Atoms lack a definite due to the probabilistic nature of the electron cloud, but the distribution can exhibit non-spherical characteristics influenced by quantum numbers and molecular contexts. For instance, in molecules, hybridization of atomic orbitals—such as sp³ hybridization in carbon—results in a tetrahedral arrangement of to minimize repulsion and optimize bonding. However, for isolated atoms, the overall electron cloud is often effectively spherical for closed shells, with deviations arising from unfilled orbitals. Direct visualization of atomic surfaces has been enabled by scanning tunneling microscopy (STM), invented by and in 1981, which maps variations at the atomic scale by measuring tunneling currents between a sharp tip and the sample surface. This technique provides empirical evidence of the irregular, probabilistic contours of atomic electron clouds, confirming sizes and subtle shape features in real materials.

Stability and Decay

Nuclear stability arises from the balance of attractive strong nuclear forces and repulsive forces within the nucleus, with stable isotopes exhibiting specific patterns in proton (Z) and (N) numbers. Nuclides with even values of both Z and N, known as even-even nuclei, are particularly due to nucleon pairing effects that lower their energy. Additionally, certain "magic numbers" of protons or neutrons—2, 8, 20, 28, 50, 82, and 126—correspond to filled nuclear shells, enhancing stability analogous to electron shells in atoms; nuclei with these configurations, such as (N=2, Z=2) or lead-208 (N=126, Z=82), are exceptionally long-lived. The -to-proton ratio (N/Z) also governs stability: for light nuclei (Z < 20), stable isotopes have N/Z ≈ 1, while heavier nuclei require N/Z > 1 (up to about 1.5) to counterbalance increasing Coulomb repulsion. Unstable nuclei undergo to achieve a more stable configuration, primarily through three modes: , and gamma decay. involves the emission of an , a nucleus (two protons and two neutrons), typically from heavy nuclei (Z > 82) to reduce repulsion; for example, decays via alpha emission to thorium-234. occurs in two variants: beta-minus (β⁻) emission of an and antineutrino, converting a to a proton (increasing Z by 1), or beta-plus (β⁺) emission of a and , converting a proton to a (decreasing Z by 1); this mode adjusts the N/Z ratio toward stability. Gamma decay follows or , releasing a high-energy from an excited nucleus to reach its , without altering Z or N. The energetics of decay are quantified by the Q-value, the released or absorbed, calculated as
Q=(MparentMdaughters)c2,Q = (M_\text{parent} - M_\text{daughters}) c^2,
where MM denotes atomic masses and cc is the ; a positive Q indicates an energetically favorable, . For decay to occur, Q must exceed zero, with the difference reflecting the differences between parent and daughter nuclei.
Radioactive decay follows an exponential law governed by the decay constant λ, where the number of undecayed nuclei N at time t is N=N0eλtN = N_0 e^{-\lambda t}, with N0N_0 the initial number. The half-life t1/2t_{1/2}, the time for half the nuclei to decay, relates to λ by t1/2=ln2λ0.693λt_{1/2} = \frac{\ln 2}{\lambda} \approx \frac{0.693}{\lambda}. Half-lives span vast ranges, from fractions of a second to billions of years; for instance, uranium-238 has a half-life of 4.468 billion years, making it key for geochronology. Nuclear stability also influences fission and fusion processes, determined by the per curve, which peaks at (approximately 8.80 MeV per ), near , rendering it the most stable nucleus. Lighter elements (A < 56) can release energy via fusion by forming heavier nuclei toward the peak, while heavier elements (A > 56) undergo fission to lighter, more stable fragments, also releasing energy; these thresholds explain and .

Electromagnetic Characteristics

The nuclear magnetic moment arises primarily from the intrinsic spins of protons and neutrons within the nucleus, as these nucleons possess spin angular momentum of 1/2 ħ and associated . The magnitude of this moment is quantified in units of the , defined as μ_N = ℏ / (2 m_p), where is the , ℏ is the reduced Planck's constant, and m_p is the proton mass; this unit is approximately 5.0507837 × 10^{-27} J/T. For example, the proton's is about 2.7928 μ_N, while the 's is -1.9130 μ_N, reflecting their distinct internal structures despite zero net charge for the . Electrons contribute to the atom's overall magnetic moment through both orbital and spin angular momenta. The orbital magnetic moment is given by μ_l = - (e / 2 m_e) L, where L is the orbital angular momentum vector and m_e is the electron mass; its magnitude is on the order of the Bohr magneton, μ_B = e ℏ / (2 m_e) ≈ 9.274 × 10^{-24} J/T./University_Physics_III_-Optics_and_Modern_Physics(OpenStax)/08%3A_Atomic_Structure/8.03%3A_Orbital_Magnetic_Dipole_Moment_of_the_Electron) The spin magnetic moment is μ_s = - g (e / 2 m_e) S, with S the spin angular momentum (1/2 ħ for an electron) and g ≈ 2.0023 the electron g-factor, making it approximately twice the Bohr magneton in effective strength./University_Physics_III_-Optics_and_Modern_Physics(OpenStax)/08%3A_Atomic_Structure/8.03%3A_Orbital_Magnetic_Dipole_Moment_of_the_Electron) These moments couple vectorially in atoms with unpaired electrons, influencing the total atomic magnetism. Atomic manifests as or depending on pairing. occurs in atoms with all s paired, such as or , where the induced orbital currents oppose an applied , resulting in weak repulsion. arises in atoms with unpaired s, like the oxygen atom (which has two unpaired 2p s in its ), where the permanent magnetic moments align with the field, producing weak attraction. The Zeeman effect demonstrates these magnetic interactions by causing the splitting of atomic energy levels in an external . In the normal Zeeman effect, observed in atoms without electron spin consideration, spectral lines split into 2l + 1 components due to the field's on the orbital , with energy shifts ΔE = μ_B B m_l, where B is the field strength and m_l the . The anomalous Zeeman effect, more relevant for most atoms, incorporates electron spin, leading to finer splitting patterns proportional to the total g_J μ_B B m_J, where g_J is the ./08%3A_The_Hydrogen_Atom/8.04%3A_Magnetic_Properties_and_the_Zeeman_Effect) In atoms, permanent electric dipole moments are typically absent in ground states due to parity conservation, which forbids a static charge separation in spherical symmetric configurations. However, transient electric moments arise from temporary fluctuations in distribution, as seen in the dynamic motion of electrons around the nucleus, enabling interactions like van der Waals forces between atoms. These transient moments can also be induced by external , polarizing the atom and creating an effective proportional to the field strength and atomic ./Physical_Properties_of_Matter/Atomic_and_Molecular_Properties/Dipole_Moments)

Chemical Behavior

Valence and Reactivity

Valence electrons are the electrons occupying the outermost of an atom, which primarily dictate its chemical reactivity and placement within the periodic table groups. These electrons are the ones available for participation in chemical reactions, as they are farthest from the positively charged nucleus and thus least tightly bound. For instance, sodium (Na), with an atomic number of 11, has a single in its 3s orbital, making it prone to losing that electron to achieve stability. In contrast, , with an atomic number of 17, possesses seven valence electrons in its 3s and 3p orbitals, driving it to gain one more electron for completion. The describes the tendency of atoms to achieve a stable configuration by acquiring, losing, or sharing to fill their valence shell with eight , mimicking the full outer shell of . This principle underpins much of chemical bonding and reactivity, often visualized through Lewis structures that depict valence as dots around atomic symbols to illustrate electron distribution and stability. Exceptions exist for elements like (which seeks a of two ) or those beyond the second period that can expand their octet, but the rule holds for most main-group elements. Electronegativity quantifies an 's power to attract bonding electrons toward itself, with the Pauling scale—developed by in 1932—serving as the standard measure. On this scale, values range from about 0.7 for cesium to 4.0 for , the most electronegative element, reflecting its strong electron-pulling ability due to high nuclear charge and small atomic size. Higher electronegativity correlates with greater reactivity in forming bonds, particularly for nonmetals. Reactivity patterns across the periodic table stem directly from counts: metals in Group 1, with one , exhibit high reactivity by easily donating it to form positive ions, increasing down the group as atomic size grows and becomes easier. Conversely, in Group 18, with eight s (a complete octet), display chemical inertness under standard conditions, resisting reactions due to their stable —though rare compounds like fluorides exist under extreme settings. Transition metals, such as iron, show variable reactivity through multiple oxidation states, like +2 and +3, allowing them to participate in diverse reactions by losing different numbers of d-electrons alongside s-electrons.

Bonding Mechanisms

Atoms form bonds through interactions involving their valence electrons, which enable the sharing or transfer of electrons to achieve stable electron configurations. These mechanisms include ionic, covalent, metallic, and weaker interactions such as coordinate bonds and van der Waals forces, each dictating the structure and properties of resulting compounds or materials. Ionic bonding occurs when atoms transfer electrons from a metal to a nonmetal, forming positively charged cations and negatively charged anions that are held together by electrostatic attractions in a crystalline lattice. This electron transfer results in ions with noble gas configurations, stabilizing the structure. The strength of ionic bonds is quantified by lattice energy, the energy released when gaseous ions form the solid lattice, approximated by the formula U=kq1q2rU = \frac{k q_1 q_2}{r}, where kk is Coulomb's constant, q1q_1 and q2q_2 are the ion charges, and rr is the interionic distance; higher charges and smaller distances yield stronger bonds. For example, in sodium chloride (NaCl), the lattice energy is approximately 788 kJ/mol, reflecting the robust attraction between Na⁺ and Cl⁻ ions. Covalent bonding involves the sharing of electron pairs between atoms, typically nonmetals, to fill their valence shells and form molecules. In this mechanism, atoms overlap their atomic orbitals, creating shared pairs that localize between nuclei, as described by , while (MO) theory provides a more delocalized view where electrons occupy spanning the atoms. , a measure of bond strength, is calculated in MO theory as half the difference between the number of bonding and antibonding electrons; for instance, in the H₂ molecule, two electrons in a bonding orbital yield a bond order of 1. This sharing leads to directional bonds, influencing molecular shapes. Metallic bonding arises in metals, where valence electrons are delocalized and free to move throughout a lattice of positively charged metal ions, providing cohesion and explaining properties like conductivity and malleability. The "sea of electrons" model describes these delocalized electrons as the binding force, with bond strength increasing with the number of electrons contributed per atom; for example, in , each atom donates one to the conduction band, forming a metallic . This delocalization allows electrons to respond to external fields, enabling high electrical and conductivity. Coordinate, or dative, bonds are a subtype of covalent bonding where both electrons in the shared pair are donated by one atom, often from a Lewis base to a Lewis acid, such as in the (NH₄⁺) where provides the pair to a proton. These bonds are equivalent in strength to regular covalent bonds once formed but originate from unequal electron contribution. Weaker intermolecular forces, known as van der Waals forces, include dispersion forces from temporary dipoles and dipole-dipole interactions, which are significantly less energetic (typically 1-10 kJ/mol) than covalent or ionic bonds and contribute to cohesion in nonpolar substances like or hydrocarbons. The valence shell electron pair repulsion (VSEPR) theory predicts molecular geometries arising from atomic bonds by considering the repulsion between electron pairs around a central atom, arranging them to minimize repulsion and determining bond angles. For example, in water (H₂O), four electron pairs around oxygen adopt a tetrahedral electron geometry, resulting in a bent molecular shape with a 104.5° bond angle due to two lone pairs. This model applies primarily to covalent and coordinate bonding, providing insight into how atomic interactions dictate three-dimensional structures.

Ionization and Excitation

Ionization refers to the process by which an is removed from an atom, requiring a specific minimum known as the (IE), which is the energy needed to detach the most loosely bound from a neutral atom in the gas phase. For the , the first ionization energy is precisely 13.59844 eV, corresponding to the transition from the (n=1) to the continuum. This value arises from the of the in the 1s orbital and serves as a fundamental benchmark in . Across the periodic table, the first ionization energy generally increases from left to right within a period due to the increasing , which pulls electrons more tightly toward the nucleus while the principal remains constant. Successive ionization energies, which measure the energy required to remove additional electrons from an already ionized species, increase significantly with each step because subsequent electrons are removed from increasingly positive ions with higher effective nuclear charges. For sodium (Na), the first IE is 5.139 eV, removing the valence 3s electron, while the second IE jumps to 47.286 eV to remove a core 2p electron, reflecting the greater stability of the filled inner shell. This sharp rise occurs due to the need to break into a lower-energy electron shell, making further ionization much more energetically costly. These values highlight how atomic structure, particularly shell configurations, dictates the energetics of ion formation. Excitation involves absorbing energy to promote an from a lower to a higher unoccupied orbital within the atom, without removing it entirely, leading to discrete energy levels observable in absorption spectra. For -like atoms, the wavelengths of these transitions follow the , which empirically describes the spectral lines arising from such excitations: 1λ=R(1n121n22)\frac{1}{\lambda} = R \left( \frac{1}{n_1^2} - \frac{1}{n_2^2} \right) where λ\lambda is the wavelength, RR is the (approximately 1.097 × 10^7 m^{-1} for ), and n1<n2n_1 < n_2 are the principal quantum numbers of the initial and final states, respectively. This formula originates from early spectroscopic observations and was later derived theoretically in the Bohr model, providing a cornerstone for understanding atomic energy quantization. These excitations typically involve transitions between electron shells, such as from n=1 to n=2 in . In high-temperature environments like stellar interiors, atoms often exist in plasma states where thermal energies exceed ionization potentials, resulting in highly ionized species with multiple electrons stripped away. For instance, in the cores of stars, elements such as iron can reach states like Fe^{16+} or higher, contributing to the opacity and energy transport in stellar atmospheres through their complex ionization and excitation dynamics. These plasmas, fully or partially ionized gases, dominate the baryonic matter in the universe and influence processes like nuclear fusion. Photoionization, a specific mechanism of ionization, occurs when an atom absorbs a photon with energy equal to or greater than its ionization potential, ejecting an electron with the excess energy as kinetic energy. The probability of this process is quantified by the photoionization cross-section, which varies with photon energy and peaks near the ionization threshold before decreasing at higher energies due to the angular momentum dependence of the ejected electron. Databases of these cross-sections for atoms from hydrogen to heavy elements enable modeling of astrophysical and laboratory plasmas, with values for hydrogen showing a threshold at 13.6 eV and a cross-section on the order of 6 × 10^{-18} cm² just above it.

Identification Methods

Spectroscopic Techniques

Spectroscopic techniques exploit the interaction of electromagnetic radiation with atoms to probe their electronic structure and composition, revealing unique spectral signatures that enable identification of elements. In atomic emission spectroscopy, excited atoms emit light at discrete wavelengths corresponding to transitions between quantized energy levels, producing line spectra characteristic of each element. These emission lines arise when electrons drop from higher to lower energy states, releasing photons of specific energies. Similarly, atomic absorption spectroscopy measures the absorption of light by ground-state atoms, where the absorbed wavelengths match the energy differences between levels, creating dark lines in a continuous spectrum. The uniqueness of these line spectra serves as a fingerprint for elemental identification, as no two elements share identical patterns. For instance, the Balmer series in hydrogen consists of visible emission lines from transitions to the n=2 level, such as the red H-alpha line at 656 nm. The historical foundations of these techniques trace back to the early 19th century, when Joseph von Fraunhofer observed hundreds of dark absorption lines in the solar spectrum in 1814, now known as , which represent atomic absorption by elements in the Sun's atmosphere and Earth's air. These observations laid the groundwork for understanding atomic spectra as tools for composition analysis. By the late 19th century, such spectral data contributed to the development of the ; Dmitri Mendeleev's predictions of undiscovered elements included anticipated spectral properties that aligned with later observations, reinforcing the table's predictive power when new elements were identified through their unique line patterns. External fields perturb these spectral lines, providing deeper insights into atomic structure. The Zeeman effect, discovered in 1896, describes the splitting of spectral lines into multiple components when atoms are placed in a magnetic field, due to the interaction between the field and the atom's magnetic moment from electron orbital motion. This effect, observed in emission lines of elements like sodium and cadmium, allows measurement of atomic magnetic properties and was key in confirming electron charge-to-mass ratios. Complementarily, the Stark effect, identified in 1913, involves the splitting and shifting of lines under an electric field, arising from the field's coupling to the atom's electric dipole moment, particularly pronounced in hydrogen-like spectra. These perturbations enable precise studies of energy level fine structure and are essential for high-resolution atomic identification in varying environments. Laser-induced fluorescence (LIF) enhances sensitivity in atomic analysis by selectively exciting atoms with tuned laser light to higher energy states, followed by detection of the resulting fluorescence as atoms relax. This technique achieves sub-parts-per-billion detection limits for elements in gases or vapors, leveraging the high intensity and monochromaticity of lasers to minimize background interference and enable spatially resolved measurements. LIF is particularly valuable for real-time, non-intrusive probing in complex matrices, such as atmospheric or combustion environments. For heavier elements and inner-shell studies, X-ray spectroscopy targets transitions involving core electrons. In X-ray emission, inner-shell vacancies created by high-energy excitation are filled by outer electrons, producing characteristic lines like the K-alpha, which results from an L-shell (n=2) electron dropping to the K-shell (n=1), with wavelengths unique to each element's nuclear charge. These lines, such as copper's K-alpha at about 1.54 Å, facilitate non-destructive elemental mapping in materials, as the energies scale with atomic number squared, allowing unambiguous identification across the periodic table./University_Physics_III_-Optics_and_Modern_Physics(OpenStax)/08%3A_Atomic_Structure/8.06%3A_Atomic_Spectra_and_X-rays)

Isotopic Analysis

Isotopic analysis encompasses methods that exploit mass differences and nuclear properties to identify and quantify atomic isotopes, providing insights into sample composition, age, and environmental history. These techniques are essential for distinguishing stable and radioactive isotopes without altering their nuclear structure, often achieving high precision through instrumental separation or spectroscopic detection. Mass spectrometry is a primary tool for isotopic analysis, ionizing atoms or molecules and separating them based on their mass-to-charge ratio (m/z) using electric or magnetic fields. In isotope ratio mass spectrometry (IRMS), ions are accelerated and deflected proportionally to their mass, allowing precise measurement of isotopic abundances in gases like CO₂ for carbon and oxygen isotopes. For example, stable isotope analysis of water samples employs conventional IRMS after conversion to gaseous forms, enabling detection of subtle variations in hydrogen and oxygen isotopes for hydrological studies. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry extends this to large biomolecules, where a laser desorbs and ionizes samples embedded in a matrix, facilitating isotopic labeling for metabolic tracing with high spatial resolution in tissues. Recent advancements in MALDI2 enhance sensitivity for stable isotope imaging, supporting applications in biology and geochemistry. Nuclear magnetic resonance (NMR) spectroscopy distinguishes isotopes through differences in nuclear spin and chemical environment, producing unique chemical shifts. For hydrogen isotopes, ¹H NMR detects protium (¹H) signals, while ²H NMR identifies deuterium (²H) due to its spin-1 nucleus and lower gyromagnetic ratio, resulting in distinct resonance frequencies. Quantitative ²H NMR, using methods like ERETIC for internal referencing, accurately determines deuterium isotope ratios in labeled compounds without additional calibration standards. Isotope effects on chemical shifts further aid analysis, as deuterium substitution alters hydrogen bonding patterns, observable in spectra for structural elucidation. Analysis of stable isotope ratios provides non-destructive tracers for environmental and chronological studies. Carbon-13 (¹³C) ratios in organic remains, measured via IRMS, reveal dietary sources or age in archaeological contexts, with δ¹³C values indicating C3 versus C4 plant contributions. Oxygen-18 (¹⁸O) ratios in carbonates or ice cores proxy paleoclimate, where higher δ¹⁸O values correlate with warmer temperatures due to evaporation preferences for lighter isotopes. These ratios are expressed in per mil (‰) deviations from standards like VPDB for carbon, enabling global syntheses of foraminiferal data for oceanographic reconstructions. Radiometric dating quantifies radioactive isotopes by measuring parent-daughter ratios accumulated over time. The uranium-lead (U-Pb) method analyzes decay of ²³⁸U to ²⁰⁶Pb (half-life 4.468 billion years) and ²³⁵U to ²⁰⁷Pb (half-life 703.8 million years) in zircon crystals, providing concordant ages for rocks older than 1 million years with 0.1–1% precision. This dual decay chain cross-validates results, minimizing errors from initial lead or loss, and has dated Earth's oldest materials to over 4 billion years. Fractional distillation enriches isotopes by exploiting boiling point differences in volatile compounds. For oxygen, water is distilled in multistage columns, where heavier H₂¹⁸O condenses preferentially, achieving enrichments up to 90 ppm in ¹⁸O as measured by IRMS. Historically, this method concentrated heavy water isotopes since the 1930s, with column designs optimizing reflux for large-scale separation of deuterium and oxygen isotopes.

Origins and Abundance

Cosmological Formation

The formation of atomic nuclei, the precursors to atoms, began in the early universe through Big Bang nucleosynthesis (BBN), which occurred approximately 100 to 200 seconds after the when the universe had cooled to temperatures around 0.1 MeV, allowing protons and neutrons to combine into light nuclei. During BBN, primarily hydrogen-1 (protons), helium-4, and trace amounts of deuterium, helium-3, and lithium-7 were produced, with helium-4 reaching a primordial mass fraction of about 25%, while hydrogen dominated at roughly 75% by mass. This process was limited by the rapid expansion and cooling of the universe, preventing the synthesis of heavier elements beyond beryllium. Neutral atoms formed much later, during the epoch of recombination approximately 380,000 years after the Big Bang, when the universe had cooled to about 3,000 K (0.26 eV). At this point, the density of free electrons dropped sufficiently for them to combine with nuclei, primarily hydrogen and helium, forming stable neutral atoms and releasing the cosmic microwave background radiation. Subsequent atomic nucleus formation occurred through stellar nucleosynthesis, where stars fuse lighter elements into heavier ones over billions of years. In low-mass stars like the Sun, the proton-proton (pp) chain converts hydrogen into helium-4 via a series of beta decays and fusions, dominating energy production in stellar cores at temperatures around 15 million K. In more massive stars, the CNO (carbon-nitrogen-oxygen) cycle, which uses carbon, nitrogen, and oxygen as catalysts, efficiently fuses hydrogen into helium at higher temperatures above 17 million K, accounting for up to 99% of hydrogen burning in stars more massive than about 1.3 solar masses. For elements heavier than iron, slow neutron capture (s-process) in asymptotic giant branch stars and red giants produces nuclei up to lead and bismuth by gradual neutron addition followed by beta decay. Supernovae and neutron star mergers play crucial roles in synthesizing elements beyond iron through explosive nucleosynthesis, particularly the rapid neutron capture (r-process), where neutron fluxes exceeding 102010^{20} cm3^{-3} enable swift capture sequences on seed nuclei, forming heavy elements like gold and uranium before beta decays stabilize them. Core-collapse supernovae from massive stars (above 8 solar masses) and binary neutron star mergers provide the extreme conditions for the r-process, ejecting these metals into the interstellar medium to enrich subsequent generations of stars. Nuclear binding energies, peaking around iron-56, make fusion of lighter elements exothermic while fission of heavier ones releases energy, driving these cosmic synthesis processes. Observations of the cosmic microwave background (CMB) provide independent constraints on BBN by measuring the baryon-to-photon ratio η6×1010\eta \approx 6 \times 10^{-10}, which aligns with primordial abundances predicted by standard BBN models, confirming the light element yields within 1-2% precision. Recent James Webb Space Telescope (JWST) observations since 2022 have revealed surprisingly high metallicities in galaxies at redshifts z>68z > 6-8, indicating rapid early enrichment from the first supernovae and mergers just 300-500 million years after the , consistent with r-process contributions from Population III stars.

Terrestrial Distribution

The distribution of atomic elements on Earth reflects both primordial inheritance from the solar system's formation and subsequent geological, biological, and atmospheric processes that have differentiated and cycled these elements across the planet's crust, mantle, oceans, and biosphere. In the Earth's crust, oxygen is the most abundant element by mass, comprising approximately 46.6%, primarily bound in silicates and oxides, while iron ranks fourth at about 5%, concentrated in minerals like hematite and magnetite. Compared to the solar system's bulk composition—approximated by carbonaceous chondrites—Earth shows depletions in volatile elements such as hydrogen, carbon, and nitrogen due to thermal processing and accretion dynamics, whereas refractory elements like oxygen, silicon, magnesium, and iron maintain relative similarities to solar abundances. Geochemical cycles govern the movement and transformation of key elements, maintaining Earth's . The carbon cycle involves the exchange of carbon atoms among the atmosphere (as CO₂), (through and respiration), oceans (via dissolution and biological uptake), and (in sediments and rocks), with fluxes estimated at around 120 gigatons of carbon per year through terrestrial alone. Similarly, the converts atmospheric N₂ (fixed by microbes and into bioavailable forms like ) through processes including , , and assimilation in soils and waters, cycling approximately 140 million tons annually via biological fixation. The , or hydrologic cycle, circulates and oxygen atoms primarily as H₂O, driven by evaporation from oceans (contributing 86% of global moisture), condensation into clouds, and , with total annual over land reaching about 119,000 cubic kilometers. Biologically, certain elements are indispensable for life, forming the core of organic molecules and metabolic processes. The macronutrients carbon, hydrogen, oxygen, , phosphorus, and —collectively known as CHNOPS—constitute over 99% of living by mass, serving as building blocks for proteins, nucleic acids, , and carbohydrates. Trace metals play critical roles as well; for instance, iron atoms in enable oxygen transport in blood by binding O₂ reversibly in its ferrous (Fe²⁺) state, with humans requiring about 1-2 milligrams daily to maintain adequate levels. In the atmosphere, dominates at 78% by volume as N₂, inert and essential for diluting oxygen, while O₂ comprises 21%, supporting aerobic respiration and forming the . Human activities have significantly altered elemental distributions, exacerbating geochemical imbalances. Mining for metals like iron and rare earth elements (REEs) has redistributed crustal abundances, with global extraction exceeding 2.5 billion tons annually, often leading to and habitat loss. from REE mining, concentrated in regions like China's Bayan Obo deposit, releases toxic byproducts including and radioactive , contaminating water and soils and bioaccumulating in ecosystems, with detected REE levels in local populations' blood and urine indicating health risks such as respiratory and neurological damage. These interventions disrupt natural cycles, for example, by increasing atmospheric CO₂ through combustion and nitrogen loading via fertilizers, which has amplified in aquatic systems.

Rare and Exotic Variants

Superheavy elements represent the frontier of atomic synthesis, where atomic numbers exceed 103, pushing beyond naturally occurring actinides. , with Z=118, was first synthesized in 2006 through the fusion of californium-249 and isotopes at the , yielding a single atom of oganesson-294 that decayed within milliseconds. These elements are produced in particle accelerators via heavy-ion collisions, but their extreme instability limits observation to fleeting instances, with half-lives often measured in microseconds. Theoretical models predict an "island of stability" for nuclei around Z=114 to 126 and neutron numbers N=172 to 184, where enhanced nuclear shell effects could extend half-lives to seconds or even years, potentially allowing chemical studies. However, current syntheses remain far from this region, with observed isotopes exhibiting rapid chains. Exotic atoms deviate from conventional electron-proton structures by incorporating other fundamental particles, enabling probes of quantum electrodynamics and nuclear forces. In muonic atoms, a negatively charged muon—207 times more massive than an electron—replaces the electron, orbiting much closer to the nucleus and amplifying electromagnetic interactions for precise nuclear radius measurements, as demonstrated in experiments with light elements like hydrogen and helium. Positronium consists of an electron and its antiparticle, a positron, bound by Coulomb attraction in a hydrogen-like configuration, with lifetimes of about 0.1 to 140 nanoseconds before annihilation into gamma rays; it serves as a testing ground for quantum relativistic effects. Antihydrogen, comprising an antiproton and a positron, mirrors hydrogen's spectrum and has been produced at CERN since 1995 by combining antiproton and positron plasmas, allowing tests of matter-antimatter symmetry through laser spectroscopy. Hints of strange matter, a hypothetical state denser than nuclear matter, emerge from recreations of quark-gluon plasma (QGP)—a deconfined phase of quarks and gluons—in high-energy collisions at the (RHIC) and (LHC) during the 2000s. At RHIC, gold ion collisions in 2005 revealed a near-perfect fluid-like QGP with jet quenching and elliptic flow, suggesting collective behavior akin to the early universe's conditions 10 microseconds after the . LHC experiments confirmed these findings with lead ion runs from 2010, producing QGP at higher temperatures (up to 5.5 trillion Kelvin) and probing strange quark enhancements in hyperons, though stable strangelets remain unobserved. Theoretical constructs extend atomic variants into speculative realms, positing substructures beyond quarks and leptons. are hypothesized point-like particles composing quarks and leptons, potentially unifying the Standard Model's 24 fermions into fewer building blocks, though no experimental evidence supports their existence despite models like the rishon preon scheme. Magnetic monopoles, isolated north or south magnetic charges, could theoretically integrate into atomic-like configurations if synthesized, altering electromagnetic interactions, but grand unified theories predict their scarcity, with searches at accelerators yielding null results. Recent advances in superheavy synthesis target element 119 (ununennium) to approach the island of stability, with attempts using titanium-50 beams on actinide targets at facilities like RIKEN and Berkeley Lab's 88-Inch Cyclotron since 2023. In 2024, Japanese researchers at RIKEN reported progress in optimizing fusion cross-sections for berkelium-249 + titanium-50, aiming for detectable yields despite half-lives under a second. Measurements of sub-microsecond half-lives, such as 60 nanoseconds for rutherfordium-252 in 2025, refine decay models and guide beam intensities, with predictions suggesting Z=119 isotopes might achieve milliseconds if neutron-rich. These efforts underscore the technological limits, requiring accelerators with intensities exceeding 10^12 ions per second.

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