Hubbry Logo
Argon compoundsArgon compoundsMain
Open search
Argon compounds
Community hub
Argon compounds
logo
7 pages, 0 posts
0 subscribers
Be the first to start a discussion here.
Be the first to start a discussion here.
Argon compounds
Argon compounds
from Wikipedia

Argon compounds, the chemical compounds that contain the element argon, are rarely encountered due to the inertness of the argon atom. However, compounds of argon have been detected in inert gas matrix isolation, cold gases, and plasmas, and molecular ions containing argon have been made and also detected in space. One solid interstitial compound of argon, Ar1C60 is stable at room temperature. Ar1C60 was discovered by the CSIRO.

Argon ionises at 15.76 eV, which is higher than hydrogen, but lower than helium, neon or fluorine.[1] Molecules containing argon can be van der Waals molecules held together very weakly by London dispersion forces. Ionic molecules can be bound by charge induced dipole interactions. With gold atoms there can be some covalent interaction.[2] Several boron-argon bonds with significant covalent interactions have been also reported.[3][4] Experimental methods used to study argon compounds have included inert gas matrices, infrared spectroscopy to study stretching and bending movements, microwave spectroscopy and far infrared to study rotation, and also visible and ultraviolet spectroscopy to study different electronic configurations including excimers. Mass spectroscopy is used to study ions.[5] Computation methods have been used to theoretically compute molecule parameters, and predict new stable molecules. Computational ab initio methods used have included CCSD(T), MP2 (Møller–Plesset perturbation theory of the second order), CIS and CISD. For heavy atoms, effective core potentials are used to model the inner electrons, so that their contributions do not have to be individually computed. More powerful computers since the 1990s have made this kind of in silico study much more popular, being much less risky and simpler than an actual experiment.[5] This article is mostly based on experimental or observational results.

The argon fluoride laser is important in photolithography of silicon chips. These lasers make a strong ultraviolet emission at 192 nm.[6]

Argonium

[edit]

Argonium (ArH+) is an ion combining a proton and an argon atom. It is found in interstellar space in diffuse atomic hydrogen gas where the fraction of molecular hydrogen H2 is in the range of 0.0001 to 0.001.[1]

Argonium is formed when H2+ reacts with Ar atoms:[1]

Ar + H+
2
→ ArH+ + H[1]

and it is also produced from Ar+ ions produced by cosmic rays and X-rays from neutral argon:

Ar+ + H2 → *ArH+ + H[1] 1.49 eV.[7]

When ArH+ encounters an electron, dissociative recombination can occur, but it is extremely slow for lower energy electrons, allowing ArH+ to survive for a much longer time than many other similar protonated cations.

ArH+ + e → ArH* → Ar + H[1]

Artificial ArH+ made from earthly Ar contains mostly the isotope 40Ar rather than the cosmically abundant 36Ar. Artificially it is made by an electric discharge through an argon-hydrogen mixture.[8]

Natural occurrence

[edit]

In the Crab Nebula, ArH+ occurs in several spots revealed by emission lines. The strongest place is in the Southern Filament. This is also the place with the strongest concentration of Ar+ and Ar2+ ions.[7] The column density of ArH+ in the Crab Nebula is between 1012 and 1013 atoms per square centimeter.[7] Possibly the energy required to excite the ions so that then can emit, comes from collisions with electrons or hydrogen molecules.[7] Towards the Milky Way centre the column density of ArH+ is around 2×1013 cm−2.[1]

Cluster argon cations

[edit]

The diargon cation, Ar+
2
has a binding energy of 1.29 eV.[9]

The triargon cation Ar+
3
is linear, but has one Ar−Ar bond shorter than the other. Bond lengths are 2.47 and 2.73 ångströms. The dissociation energy to Ar and Ar2+ is 0.2 eV. In line with the molecule's asymmetry, the charge is calculated as +0.10, +0.58 and +0.32 on each argon atom, so that it greatly resembles Ar+
2
bound to a neutral Ar atom.[10]

Larger charged argon clusters are also detectable in mass spectroscopy. The tetraargon cation is also linear. Ar+
13
icosahedral clusters have an Ar+
3
core, whereas Ar+
19
is dioctahedral with an Ar+
4
core. The linear Ar+
4
core has +0.1 charge on the outer atoms, and +0.4 charge on each or the inner atoms. For larger charged argon clusters, the charge is not distributed on more than four atoms. Instead the neutral outer atoms are attracted by induced electric polarization.[11] The charged argon clusters absorb radiation, from the near infrared, through visible to ultraviolet. The charge core, Ar+
2
, Ar+
3
or Ar+
4
is called a chromophore. Its spectrum is modified by the first shell of neutral atoms attached. Larger clusters have the same spectrum as the smaller ones. When photons are absorbed in the chromophore, it is initially electronically excited, but then energy is transferred to the whole cluster in the form of vibration. Excess energy is removed by outer atoms evaporating from the cluster one at a time. The process of destroying a cluster by light is called photofragmentation.[11]

Negatively-charged argon clusters are thermodynamically unstable, and therefore cannot exist. Argon has a negative electron affinity.[11]

Argon monohydride

[edit]

Neutral argon hydride, also known as argon monohydride (ArH), was the first discovered noble gas hydride. J. W. C. Johns discovered an emission line of ArH at 767 nm and announced the find in 1970. The molecule was synthesized using X-ray irradiation of mixtures of argon with hydrogen-rich molecules such as H2, H2O, CH4 and CH3OH.[12] The X-ray excited argon atoms are in the 4p state.[13]

Argon monohydride is unstable in its ground state, 4s, as a neutral inert gas atom and a hydrogen atom repel each other at normal intermolecular distances. When a higher-energy-level ArH* emits a photon and reaches the ground state, the atoms are too close to each other, and they repel and break up. However a van der Waals molecule can exist with a long bond.[14] However, excited ArH* can form stable Rydberg molecules, also known as excimers. These Rydberg molecules can be considered as a protonated argon core, surrounded by an electron in one of many possible higher energy states.[15]

Formation: Ar + ν → Ar*;  Ar* + H2 → ArH* + H[12]

Instead of dihydrogen, other hydrogen containing molecules can also have a hydrogen atom abstracted by excited argon, but note that some molecules bind hydrogen too strongly for the reaction to proceed. For example, acetylene will not form ArH this way.[12]

In the van der Waals molecule of ArH, the bond length is calculated to be about 3.6 Å and the dissociation energy calculated to be 0.404 kJ/mol (33.8 cm−1).[16] The bond length in ArH* is calculated as 1.302 Å.[17]

The spectrum of argon monohydride, both ArH* and ArD*, has been studied. The lowest bound state is termed A2Σ+ or 5s. Another low lying state is known as 4p, made up of C2Σ+ and B2π states. Each transition to or from higher level states corresponds to a band. Known bands are 3p → 5s, 4p → 5s, 5p → 5s (band origin 17486.527 cm−1[18]), 6p → 5s (band origin 21676.90 cm−1[18]) 3dσ → 4p, 3dπ → 4p (6900 cm−1), 3dδ → 4p (8200–8800 cm−1), 4dσ → 4p (15075 cm−1), 6s → 4p (7400–7950 cm−1), 7s → 4p (predicted at 13970 cm−1, but obscured), 8s → 4p (16750 cm−1), 5dπ → 4p (16460 cm−1), 5p → 6s (band origin 3681.171 cm−1),[19] 4f → 5s (20682.17 and 20640.90 cm−1 band origin for ArD and ArH), 4f → 3dπ (7548.76 and 7626.58 ccm−1), 4f → 3dδ (6038.47 and 6026.57 cm−1), 4f → 3dσ (4351.44 cm−1 for ArD).[14] The transitions going to 5s, 3dπ → 5s and 5dπ → 5s, are strongly predissociated, blurring out the lines.[19] In the UV spectrum a continuous band exists from 200 to 400 nm. This band is due to two different higher states: B2Π → A2Σ+ radiates over 210–450 nm, and E2Π → A2Σ+ is between 180 and 320 nm.[20] A band in the near infrared from 760 to 780 nm.[21]

Other ways to make ArH include a Penning-type discharge tube, or other electric discharges. Yet another way is to create a beam of ArH+ (argonium) ions and then neutralize them in laser-energized caesium vapour. By using a beam, the lifetimes of the different energy states can be observed, by measuring the profile of electromagnetic energy emitted at different wavelengths.[22] The E2π state of ArH has a radiative lifetime of 40 ns. For ArD the lifetime is 61 ns. The B2Π state has a lifetime of 16.6 ns in ArH and 17 ns in ArD.[20]

Argon polyhydrides

[edit]

The argon dihydrogen cation ArH+
2
has been predicted to exist and to be detectable in the interstellar medium. However it has not been detected as of 2021.[23] ArH+
2
is predicted to be linear in the form Ar−H−H. The H−H distance is 0.94 Å. The dissociation barrier is only 2 kcal/mol (8 kJ/mol), and ArH+
2
readily loses a hydrogen atom to yield ArH+.[24] The force constant of the ArH bond in this is 1.895 mdyne2 (1.895×1012 Pa).[25]

The argon trihydrogen cation ArH+
3
has been observed in the laboratory.[23][26] ArH2D+, ArHD+
2
and ArD+
3
have also been observed.[27] The argon trihydrogen cation is planar in shape, with an argon atom off the vertex of a triangle of hydrogen atoms.[28]

Argoxonium

[edit]

The argoxonium ion ArOH+ is predicted to be bent molecular geometry in the 11A′ state. 3Σ is a triplet state 0.12 eV higher in energy, and 3A″ is a triplet state 0.18 eV higher. The Ar−O bond is predicted to be 1.684 Å long[23] and to have a force constant of 2.988 mdyne/Å2 (2.988×1012 Pa).[25]

ArNH+

[edit]

ArNH+ is a possible ionic molecule to detect in the lab, and in space, as the atoms that compose it are common. ArNH+ is predicted to be more weakly bound than ArOH+, with a force constant in the Ar−N bond of 1.866 mdyne/Å2 (1.866×1012 Pa). The angle at the nitrogen atom is predicted to be 97.116°. The Ar−N lengths should be 1.836 Å and the N−H bond length would be 1.046 Å[25][29]

Argon dinitrogen cation

[edit]

The argon dinitrogen linear cationic complex has also been detected in the lab:

Ar + N+
2
ArN+
2
photodissociation Ar+ + N2.[23]

The dissociation yields Ar+, as this is a higher-energy state.[9] The binding energy is 1.19 eV.[9] The molecule is linear. The distance between two nitrogen atoms is 1.1 Å. This distance is similar to that of neutral N2 rather than that of N+
2
ion. The distance between one nitrogen and the argon atom is 2.2 Å.[9] The vibrational band origin for the nitrogen bond in ArN+
2
(V = 0 → 1) is at 2272.2564 cm−1 compared with N2+ at 2175 and N2 at 2330 cm−1.[9]

In the process of photodissociation, it is three times more likely to yield Ar+ + N2 compared to Ar + N+
2
.[30]

ArHN+
2

[edit]

ArHN+
2
has been produced in a supersonic jet expansion of gas and detected by Fourier transform microwave spectroscopy.[26] The molecule is linear, with the atoms in the order Ar−H−N−N. The Ar−H distance is 1.864 Å. There is a stronger bond between hydrogen and argon than in ArHCO+.[31]

The molecule is made by the following reaction:

ArH+ + N2ArHN+
2
.[31]

Bis(dinitrogen) argon cation

[edit]

The argon ion can bond two molecules of dinitrogen (N2) to yield an ionic complex with a linear shape and structure N=N−+Ar−N=N. The N=N bond length is 1.1014 Å, and the nitrogen to argon bond length is 2.3602 Å. 1.7 eV of energy is required to break this apart to N2 and ArN+
2
. The band origin of an infrared band due to antisymmetric vibration of the N=N bonds is at 2288.7272 cm−1. Compared to N2 it is redshifted 41.99 cm−1. The ground state rotational constant of the molecule is 0.034296 cm−1.[30]

Ar(N
2
)+
2
is produced by a supersonic expansion of a 10:1 mixture of argon with nitrogen through a nozzle, which is impacted by an electron beam.[30]

ArN2O+

[edit]

ArN2O+ absorbs photons in four violet–ultraviolet wavelength bands leading to breakup of the molecule. The bands are 445–420, 415–390, 390–370, and 342 nm.[32][33]

ArHCO+

[edit]

ArHCO+ has been produced in a supersonic-jet expansion of gas and detected by Fabry–Perot-type Fourier transform microwave spectroscopy.[26][34]

The molecule is made by this reaction

ArH+ + CO → ArHCO+.[31]

ArnBO+

[edit]

BO+ forms four complexes with argon: ArBO+; two isomers of Ar2BO+ (one with equidistant Ar-B bonds and another with a short and long bond); and Ar3BO+. These ions were formed by firing a green laser at a boron target in a gaseous mixture of helium, argon and nitrous oxide.[35]

Carbon dioxide–argon ion

[edit]

ArCO+
2
can be excited to form ArCO+
2
* where the positive charge is moved from the carbon dioxide part to the argon. This molecule may occur in the upper atmosphere. Experimentally the molecule is made from a low-pressure argon gas with 0.1% carbon dioxide, irradiated by a 150 V electron beam. Argon is ionized, and can transfer the charge to a carbon dioxide molecule.[36] The dissociation energy of ArCO+
2
is 0.26 eV.[36]

ArCO+
2
+ CO2 → Ar + CO
2
·CO+
2
(yields 0.435 eV.)[36]

Van der Waals molecules

[edit]

Neutral argon atoms bind very weakly to other neutral atoms or molecules to form van der Waals molecules. These can be made by expanding argon under high pressure mixed with the atoms of another element. The expansion happens through a tiny hole into a vacuum, and results in cooling to temperatures a few degrees above absolute zero. At higher temperatures the atoms will be too energetic to stay together by way of the weak London dispersion forces. The atoms that are to combine with argon can be produced by evaporation with a laser or alternatively by an electric discharge. The known molecules include AgAr, Ag2Ar, NaAr, KAr, MgAr, CaAr, SrAr, ZnAr, CdAr, HgAr, SiAr,[37] InAr, CAr,[38] GeAr,[39] SnAr,[40] and BAr.[41] SiAr was made from silicon atoms derived from Si(CH3)4.[42]

In addition to the very weakly bound van der Waals molecules, electronically excited molecules with the same formula exist. As a formula these can be written ArX*, with the "*" indicating an excited state. The atoms are much more strongly bound with a covalent bond. They can be modeled as an ArX+ surrounded by a higher energy shell with one electron. This outer electron can change energy by exchanging photons and so can fluoresce. The widely used argon fluoride laser makes use of the ArF* excimer to produce strong ultraviolet radiation at 192 nm. The argon chloride laser using ArCl* produces even shorter ultraviolet at 175 nm, but is too feeble for application.[43] The argon chloride in this laser comes from argon and chlorine molecules.[44]

Argon clusters

[edit]

Cooled argon gas can form clusters of atoms. Diargon, also known as the argon dimer, has a binding energy of 0.012 eV, but the Ar13 and Ar19 clusters have a sublimation energy (per atom) of 0.06 eV. For liquid argon, which could be written as Ar, the energy increases to 0.08 eV. Clusters of up to several hundred argon atoms have been detected. These argon clusters are icosahedral in shape, consisting of shells of atoms arranged around a central atom. The structure changes for clusters with more than 800 atoms to resemble a tiny crystal with a face-centered cubic (fcc) structure, as in solid argon. It is the surface energy that maintains an icosahedral shape, but for larger clusters internal pressure will attract the atoms into an fcc arrangement.[11] Neutral argon clusters are transparent to visible light.[11]

Diatomic van der Waals molecules

[edit]
Molecule Binding energy
ground Σ state
(cm−1)
Binding energy
excited Π state
(cm−1)
Ground state
bond length
(Å)
Excited state
bond length
(Å)
CAS number[45]
ArH 30736-04-0
ArHe 12254-69-2
LiAr 42.5 925 4.89 2.48[46]
BAr 149358-32-7
ArNe 12301-65-4
NaAr 40 560 56633-38-6
MgAr 44 246 72052-59-6
AlAr 143752-09-4
SiAr[47]
ArCl 54635-29-9
Ar2 12595-59-4
KAr 42 373 12446-47-8
CaAr 62 134 72052-60-9
SrAr 68 136
NiAr 401838-48-0
ZnAr 96 706 72052-61-0
GaAr 149690-22-2
GeAr[39]
KrAr 51184-77-1
AgAr 90 1200
CdAr[48] 106 544 72052-62-1
InAr[49] 146021-90-1
SnAr[40]
ArXe 58206-67-0
AuAr 195245-92-2
HgAr 131 446 87193-95-1

ArO* is also formed when dioxygen trapped in an argon matrix is subjected to vacuum ultraviolet. It can be detected by its luminescence:

O2 + hvO+
2
+ e;  O+
2
+ e → 2O*;  O* + Ar → ArO*.[50]

Light emitted by ArO* has two main bands, one at 2.215 eV, and a weaker one at 2.195 eV.[51]

Argon sulfide, ArS* luminesces in the near infrared at 1.62 eV. ArS is made from UV irradiated OCS in an argon matrix. The excited states lasts for 7.4 and 3.5 μs for spectrum peak and band respectively.[52]

Triatomic van der Waals molecules

[edit]

Cluster molecules containing dichlorine and more than one argon atom can be made by forcing a 95:5 mixture of helium and argon and a trace of chlorine though a nozzle. ArCl2 exists in a T shape. Ar2Cl2 has a distorted tetrahedron shape, with the two argon atoms 4.1 Å from each other, and their axis 3.9 Å from the Cl2. The van der Waals bond energy is 447 cm−1. Ar3Cl2 also exists with a van der Waals bond energy of 776 cm−1.[53]

The linear Ar·Br2 molecule has a continuous spectrum for bromine molecule X → B transitions. The spectrum of bromine is blue-shifted and spread out when it binds an argon atom.[54]

ArI2 shows a spectrum that adds satellite bands to the higher vibrational bands of I2.[55] The ArI2 molecule has two different isomers, one shape is linear, and the other is T-shaped. The dynamics of ArI2 is complex. Breakup occurs through different routes in the two isomers. The T shape undergoes intramolecular vibrational relaxation, whereas the linear one directly breaks apart.[56] Diiodine clusters, I2Arn have been made.[57]

The ArClF cluster has a linear shape.[58] The argon atom is closest to the chlorine atom.[54]

Linear ArBrCl can also rearrange to ArClBr, or a T-shaped isomer.[59]

Multiple argon atoms can "solvate" a water molecule forming a monolayer around the H2O. Ar12·H2O is particularly stable, having an icosahedral shape. Molecules from Ar·H2O to Ar14·H2O have been studied.[60]

ArBH was produced from boron monohydride (BH) which in turn was created from diborane by way of an ultraviolet 193 nm laser. The BH-argon mixture was expanded through a 0.2 mm diameter nozzle into a vacuum. The gas mixture cools and Ar and BH combine to yield ArBH. A band spectrum that combines the A1Π←X1Σ+ electronic transition, with vibration and rotation can be observed. The BH has singlet spin, and this is the first known van der Waals complex with a singlet spin pair of atoms. For this molecule the rotational constant is 0.133 cm−1, The dissociation energy is 92 cm−1 and distance from argon to boron atom is 3.70 Å.[61] ArAlH is also known to exist.[62]

MgAr2 is also known.[48]

Polyatomic van der Waals molecules

[edit]

Some linear polyatomic molecules can form T-shaped van der Waals complexes with argon. These include NCCN, carbon dioxide, nitrous oxide, acetylene, carbon oxysulfide, and ClCN. Others attach the argon atom at one end to continue to be linear, including HCN.[63]

Other polyatomic van der Waals compounds of argon, include those of fluorobenzene,[64] formyl radical (ArHCO),[65] 7-azaindole,[66] glyoxal,[67] sodium chloride (ArNaCl),[68] ArHCl,[69] and cyclopentanone.[70]

Molecule Name Ground state
binding energy
(cm−1)
Closest position or atom
to argon
Ground state
bond length of Ar
(Å)
Bond angle
from atom
(degrees)
Bond stretch force
or frequency
dipole moment D CAS number references
(CH3)2F2Si·Ar Difluorodimethylsilane – argon
CH2F2·Ar Difluoromethane – argon F 3.485 58.6 [71]
CF3CN trifluoromethylcyanide argon C1 3.73 77 947504-98-5 [72]
CF2HCH3·Ar 1,1-difluoroethane argon F [73]
CH2FCH2F·Ar 1,2-difluoroethane argon 181 F 3.576 61 264131-14-8 [74]
CH3CHO·Ar Acetaldehyde argon 161 C-1 3.567 76.34 158885-13-3 [75]
C2H4O·Ar oxirane argon 200 O 3.606 (CM) 72.34 [76]
ArBF3 Boron trifluoride argon B 3.325 on axis ArBF ≈90.5° 0.030 mdyn/Å 0.176 [77]
ArC6H6 benzene-argon on sixfold axis 3.53 from plane 0.12 [78]
ArPF3 argon phosphorus trifluoride complex P 3.953 from centre of mass 70.3° on PF2 face [79]
Ar-NCCN argon–cyanogen van der Waals complex centre of molecule 3.58 90° T shape 30 cm−1 0.0979 [63]
DCCDAr argon-deuterated acetylene centre of molecule 3.25 90° T shape 0.0008 mdyn/Å / 8.7 cm−1 [63]
SO3Ar sulfur trioxide argon S 3.350 on axis 90° from SO bond 0.059 mdyn/Å / 61 cm−1 [80]
Ar•HCCH acetylene argon T shape [81]
OCS•Ar [81]
CH3OH•Ar [81]
CH3Cl•Ar [81]
Pyridine argon [81]
Pyrrole argon [81]

Aqueous argon

[edit]

Argon dissolved in water causes the pH to rise to 8.0,[82] apparently by reducing the number of oxygen atoms available to bind protons.[83]

With ice, argon forms a clathrate hydrate. Up to 0.6 GPa, the clathrate has a cubic structure. Between 0.7 and 1.1 GPa the clathrate has a tetragonal structure. Between 1.1 and 6.0 GPa the structure is body centered orthorhombic. Over 6.1 GPa, the clathrate converts into solid argon and ice VII.[84] At atmospheric pressure the clathrate is stable below 147 K.[85] At 295 K the argon pressure from the clathrate is 108 MPa.[86]

Argon fluorohydride

[edit]

Argon fluorohydride was an important discovery in the rejuvenation of the study of noble gas chemistry. HArF is stable in solid form at temperatures below 17 K.[87] It is prepared by photolysis of hydrogen fluoride in a solid argon matrix.[88] HArArF would have such a low barrier to decomposition that it will likely never be observed.[89] However HBeArF is predicted to be more stable than HArF.[90]

Uranium compounds

[edit]

CUO in a solid argon matrix can bind one, or a few argon atoms to yield CUO·Ar, CUO·Ar3 or CUO·Ar4. CUO itself is made by evaporating uranium atoms into carbon monoxide. Uranium acts as a strong Lewis acid in CUO[88][91] and forms bonds with energies of about 3.2 kcal/mol (13.4 kJ/mol) with argon. The argon acts as a Lewis base. Its electron density is inserted into an empty 6d orbital on the uranium atom. The spectrum of CUO is changed by argon so that the U−O stretch frequency changes from 872.2 to 804.3 cm−1 and the U−C stretch frequency from 1047.3 to 852.5 cm−1.[92] The significant change in the spectrum occurs because the CUO is changed from a singlet state (in gas phase or solid neon) to a triplet state, with argon or noble gas complexing.[93] The argon–uranium bond length is 3.16 Å.[92] This is shorter than the sum of atomic radii of U and Ar of 3.25 Å, but considerably longer than a normal covalent bond to uranium. For example, U−Cl in UCl6 is 2.49 Å.[93] When xenon is included in the solid argon matrix up to a few percent, additional van der Waals molecules are formed: CUO·Ar3Xe, CUO·Ar2Xe2, CUO·ArXe3 and CUO·Xe4.[91] Similarly krypton can substitute for argon in CUO·Ar3Kr, CUO·Ar2Kr2, CUO·ArKr3 and CUO·Kr4.[93] The shape of these molecules is roughly octahedral, with a uranium centre and with the noble gas atoms around the equator.[93]

UO+
2
can bind up to five noble gas atoms in a ring around a linear O=+U=O core.[94] These molecules are produced when uranium metal is laser ablated into dioxygen. This produces UO, UO2, UO3, U+, and importantly UO+
2
. UO+
2
is then condensed into a noble gas matrix, either a pure element or a mixture. Heavier noble gas atoms will tend to displace the lighter atoms. Ionic molecules produced this way include UO
2
Ne
4
Ar+
, UO
2
Ne
3
Ar+
2
, UO
2
Ne
2
Ar+
3
, UO
2
NeAr+
4
, UO
2
Ar+
5
, UO
2
Ar
4
Kr+
, UO
2
Ar
3
Kr+
2
, UO
2
Ar
2
Kr+
3
, UO
2
ArKr+
4
, UO
2
Ar
4
Xe+
, UO
2
Ar
3
Xe+
2
, UO
2
Ar
2
Xe+
3
, and UO
2
ArXe+
4
, which are identified by a shift in the U=O antisymmetric stretching frequency.[94]

Neutral UO2 condensed in solid argon is converted from one electronic state to another by the argon atom ligands. In argon the electron configuration is 5f2(δφ) whereas in neon it is 5f17s1 (the state 3H4g compared to 3Φ2u). This is because the argon atoms have a larger antibonding interaction with the 7s1 electron, forcing it into a different subshell. The argonated compound has a stretching frequency of 776 cm−1 compared to 914.8 cm−1 in neon.[95] The argon uranium dioxide molecule is likely UO2Ar5.[96]

Beryllium oxide

[edit]

When beryllium atoms react with oxygen in a solid argon matrix (or beryllia is evaporated into the matrix) ArBeO is formed, and is observable by its infrared spectrum. The beryllia molecule is strongly polarised, and the argon atom is attracted to the beryllium atom.[93][97] The bond strength of Ar−Be is calculated to be 6.7 kcal/mol (28 kJ/mol). The Ar−Be bond length is predicted to be 2.042 Å.[98]

The cyclic Be2O2 molecule can bind two argon atoms, or one argon along with another noble gas atom.[99]

Analogously, beryllium reacting with hydrogen sulfide and trapped in an argon matrix at 4 K forms ArBeS. It has a binding energy calculated to be 12.8 kcal/mol (54 kJ/mol).[100]

ArBeO2CO (beryllium carbonate) has been prepared (along with Ne, Kr and Xe adducts).[101]

The cyclic beryllium sulfite molecule can also coordinate an argon atom onto the beryllium atom in solid neon or argon matrix.[102]

Carbonyl compounds

[edit]

Group 6 elements can form reactive pentacarbonyls that can react with argon. These were actually argon compounds discovered in 1975, and were known before the discovery of HArF, but are usually overlooked.[103] Tungsten normally forms a hexacarbonyl, but when subject to ultraviolet radiation it breaks into a reactive pentacarbonyl. When this is condensed into a noble gas matrix the infrared and UV spectrum varies considerably depending on the noble gas used. This is because the noble gas present binds to the vacant position on the tungsten atom. Similar results also occur with molybdenum and chromium.[104] Argon is only very weakly bound to tungsten in ArW(CO)5.[93][105] The Ar−W bondlength is predicted to be 2.852 Å.[104] The same substance is produced for a brief time in supercritical argon at 21 °C.[106] For ArCr(CO)5 the band maximum is at 533 nm (compared to 624 nm in neon, and 518 nm in krypton). Forming 18-electron complexes, the shift in spectrum due to different matrices was much smaller, only around 5 nm. This clearly indicates the formation of a molecule using atoms from the matrix.[5]

Other carbonyls and complexed carbonyls also have reports of bonding to argon. These include Ru(CO)2(PMe3)2Ar, Ru(CO)2(dmpe)2Ar, η6-C6H6Cr(CO)2Ar.[107] Evidence also exists for ArHMn(CO)4, ArCH3Mn(CO)4, and fac-(η2-dfepe)Cr(CO)3Ar.[5]

Other noble gas complexes have been studied by photolysis of carbonyls dissolved in liquid rare gas, possibly under pressure. These Kr or Xe complexes decay on the time scale of seconds, but argon does not seem to have been studied this way. The advantage of liquid noble gases is that the medium is completely transparent to infrared radiation, which is needed to study the bond vibration in the solute.[5]

Attempts have been made to study carbonyl–argon adducts in the gas phase, but the interaction appears to be too weak to observe a spectrum. In the gas form, the absorption lines are broadened into bands because of rotation that happens freely in a gas.[5] The argon adducts in liquids or gases are unstable as the molecules easily react with the other photolysis products, or dimerize, eliminating argon.[5]

Coinage metal monohalides

[edit]

The argon coinage metal monohalides were the first noble gas metal halides discovered, when the metal monohalide molecules were put through an argon jet. There were first found in Vancouver in 2000.[108] ArMX with M = Cu, Ag or Au and X = F,[109] Cl or Br have been prepared. The molecules are linear. In ArAuCl the Ar−Au bond is 2.47 Å, the stretching frequency is 198 cm−1 and the dissociation energy is 47 kJ/mol.[110] ArAgBr also has been made.[110] ArAgF has a dissociation energy of 21 kJ/mol.[110] The Ar−Ag bond-length in these molecules is 2.6 Å.[110] ArAgCl is isoelectronic with AgCl
2
which is better known.[110] The Ar−Cu bond length in these molecules is 2.25 Å.[110]

Transition metal oxides

[edit]

In a solid argon matrix VO2 forms VO2Ar2, and VO4 forms VO4·Ar with binding energy calculated to be 12.8 and 5.0 kcal/mol (53 and 21 kJ/mol).[111] Scandium in the form of ScO+ coordinates five argon atoms to yield ScOAr+
5
.[112] these argon atoms can be substituted by numbers of krypton or xenon atoms to yield even more mixed noble gas molecules. With yttrium, YO+ bonds six argon atoms, and these too can be substituted by varying numbers of krypton or xenon atoms.[113]

In the case of transition metal monoxides, ScO, TiO and VO do not form a molecule with one argon atom. However CrO, MnO, FeO, CoO and NiO can each coordinate one argon atom in a solid argon matrix.[114] The metal monoxide molecules can be produced by laser ablation of the metal trioxide, followed by condensation on solid argon. ArCrO absorbs at 846.3 cm−1, ArMnO at 833.1, ArFeO at 872.8, ArCoO at 846.2, Ar58NiO at 825.7 and Ar60NiO at 822.8 cm−1. All these molecules are linear.[114]

There are also claims of argon forming coordination molecules in NbO2Ar2, NbO4Ar, TaO4Ar,[115] VO2Ar2, VO4Ar,[111] Rh(η2-O2)Ar2, Rh(η2-O2)2Ar2, Rh(η2-O2)2(η1-OO)Ar.[116][117][118]

Tungsten trioxide, WO3, and tungsten dioxide mono-superoxide (η2-O2)WO2 can both coordinate argon in an argon matrix. The argon can be replaced by xenon or molecular oxygen to make xenon coordinated compounds or superoxides. For WO3Ar the binding energy is 9.4 kcal/mol and for (η2-O2)WO2 it is 8.1 kcal/mol.[119]

Other transition metal compounds

[edit]

ArNiN2 binds argon with 11.52 kcal/mol. The bending frequency of ArN2 is changed from 310.7 to 358.7 cm−1 when argon attaches to the nickel atom.[120]

Other ions

[edit]

Some other binary ions observed that contain argon include BaAr2+ and BaAr2+
2
,[121] VAr+, CrAr+, FeAr+, CoAr+, and NiAr+.[5]

Gold and silver cluster ions can bind argon. Known ions are Au
3
Ar+
, Au
3
Ar+
2
, Au
3
Ar+
3
, Au
2
AgAr+
3
and AuAg
2
Ar+
3
. These have a triangular shaped metallic core with argon bound at the vertexes.[2]

ArF+ is also known[5] to be formed in the reaction

F+
2
+ Ar → ArF+ + F

and also

Ar+ + F2 → ArF+ + F.

and also

SF2+
4
+ Ar → ArF+ + SF+
3
.[122]

The ions can be produced by ultraviolet light at 79.1 nm or less.[123] The ionisation energy of fluorine is higher than that of argon, so breakup occurs thus:

ArF+ → Ar+ + F.[124]

The millimeter wave spectrum of ArF+ between 119.0232 and 505.3155 GHz has been measured to calculate molecular constants B0 = 14.8788204 GHz, D0 = 28.718 kHz.[125] There is a possibility that a solid salt of ArF+ could be prepared with SbF
6
or AuF
6
anions.[124][126]

Excited or ionized argon atoms can react with molecular iodine gas to yield ArI+[127] Argon plasma is used as an ionisation source and carrier gas in inductively coupled plasma mass spectrometry. This plasma reacts with samples to produce monatomic ions, but also forms argon oxide (ArO+), and argon nitride (ArN+) cations, which can cause isobaric interference with detection and measurement of iron-56 (56Fe) and iron-54 (54Fe), respectively, in mass spectrometry.[128] Platinum present in stainless steel can form platinum argide (PtAr+) which interferes with the detection of uranium-234 which can be used as a tracer in aquifers.[129] Argon chloride cations can interfere with the detection of arsenic as Ar35Cl+ has a mass-to-charge ratio almost identical to that of arsenic's one stable isotope, 75As.[130] In these circumstances ArO+ may be removed by reaction with NH3.[131] Alternatively electrothermal vaporization or using helium gas can avoid these interference problems.[128] Argon can also form an anion with chlorine, ArCl,[132] though this is not a problem for mass spectrometry applications as only cations are detected.

The argon borynium ion, BAr+ is produced when BBr+ at energies between 9 and 11 eV reacts with argon atoms. 90% of the positive charge is on the argon atom.[133]

ArC+ ions can be formed when argon ions impact carbon monoxide with energies between 21 and 60 eV. However more C+ ions are formed, and when the energy is on the high side, O+ is higher.[134]

ArN+ can form when argon ions impact dinitrogen with energies between 8.2 and 41.2 eV and peaking around 35 eV. However far more N+
2
and N+ are produced.[135]

ArXe+ is held together with a strength of 1445 cm−1 when it is in the X electronic state, but 1013 cm−1 when it is in the B excited state.[33]

Metal–argon cations are called "argides". The argide ions produced during mass spectroscopy have higher intensity when the binding energy of the ion is higher. Transition elements have higher binding and ion flux intensity compared to main group elements. Argides can be formed in the plasma by excited argon atoms reacting with another element atom, or by an argon atom binding with another ion:

Ar+ + M → ArM+ + e; M+ + Ar → ArM+.[136]

Doubly charged cations, called superelectrophiles, are capable of reacting with argon. Ions produced include ArCF2+
2
ArCH+
2
, ArBF+
2
and ArBF2+
containing bonds between argon and carbon or boron.[137]

Doubly ionised acetylene HCCH2+ reacts inefficiently with argon to yield HCCAr2+. This product competes with the formation of Ar+ and argonium.[138]

The SiF2+
3
ion reacts with argon to yield ArSiF2+
2
.[139]

Ion Bond length
(Å)
Dissociation energy
(kJ/mol)[5]
Excited state
bond length (Å)
Excited state
dissociation energy
ArH+ 3.4 eV
LiAr+[136] 2.343 0.30 eV
BeAr+[136] 4100 cm−1[140]
BAr+[133] 2.590 210
ArC+[141]
ArN+[136] 3.5 2.16 eV[142]
ArO+[136]
ArF+[124] 1.637 194
NaAr+[136] 19.3
MgAr+[136] 2.88[143] 1200 cm−1[140]
AlAr+[136] 982 cm−1[144]
SiAr+[136]
ArP+[136]
ArS+[136]
ArCl+[136]
Ar+
2
[136]
CaAr+ 700 cm−1[140]
ScAr+[136]
TiAr+ 0.31eV[145]
VAr+ 2.65[146] 37,D0=2974 cm−1[143]
CrAr+ 28,D0=2340[143]
MnAr+[136] 0.149 eV[145]
FeAr+ 0.11 eV[145]
CoAr+[146] 2.385[147] 49,D0=4111 cm−1[147]
NiAr+ 53,D0=4572[143]
CuAr+[136] 0.53 eV[145]
ZnAr+ 2.72[148] 0.25 eV,[145] D0=2706 cm−1[148]
GaAr+[136]
AsAr+[136]
RbAr+[149]
SrAr+ 800[140]
ZrAr+ 2.72 D0 = 2706 cm−1[148] 3.050 1179 cm−1
NbAr+ 2.677[143] 37,D0=3106 cm−1[143]
AgAr+[136]
InAr+[150]
ArI+[127]
BaAr+ 600 cm−1[140]

Polyatomic cations

[edit]

Metal ions can also form with more than one argon atom, in a kind of argon metal cluster. Different sized metal ions at the centre of a cluster can fit different geometries of argons atoms around the ion.[150] Argides with multiple argon atoms have been detected in mass spectrometry. These can have variable numbers of argon attached, but there are magic numbers, where the complex more commonly has a particular number, either four or six argon atoms.[151] These can be studied by time of flight mass spectrometer analysis and by the photodissociation spectrum. Other study methods include Coulomb explosion analysis.[152] Argon-tagging is a technique whereby argon atoms are weakly bound to a molecule under study. It results in a much lower temperature of the tagged molecules, with sharper infra-red absorption lines. The argon-tagged molecules can be disrupted by photons of a particular wavelength.[153]

Lithium ions add argon atoms to form clusters with more than a hundred argon atoms. The clusters Li+Ar4, and Li+Ar4 are particularly stable and common. Calculations show that the small clusters are all quite symmetrical. Li+Ar2 is linear, Li+Ar3 is flat and triangular shaped with D3h symmetry, Li+Ar4 is tetrahedral, Li+Ar5 could be a square pyramid or trigonal bipyramid shape. Li+Ar6 is an octahedron shape with Li at the centre. Li+Ar7 or slightly larger clusters have a core octahedron of argon atoms with one or more triangular faces capped by other argon atoms. The bonding is much weaker, which explains their greater scarcity.[154]

Sodium forms clusters with argon atoms with peaks at numbers of 8, 10, 16, 20, 23, 25 and 29, and also at the icosahedral numbers of 47, 50, 57, 60, 63, 77, 80, 116 and 147 argon atoms. This includes the square antiprism (8) and the capped square antiprism (10 atoms).[150] In Ti+Ar1−n the argon atoms induce a mixing of the ground electronic state of 3d24s1 with 3d34s0. When a plasma of titanium in expanding argon gas is made via a laser, clusters from Ti+Ar up to Ti+Ar50 are formed. But Ti+Ar6 is much more common than all the others. In this the six argon atoms are arranged in an octahedron shape around the central titanium ion. For Ti+Ar2 DFT calculations predict it is linear, Ti+Ar3 is not even flat, and has one short and two longer Ti-Ar bonds. Ti+Ar4 is a distorted tetrahedron, with one longer Ti-Ar bond. Ti+Ar5 is an asymmetrical trigonal bipyramid shape with one bond shorter. For clusters with seven or more argon atoms, the structure contains a Ti+Ar6 octahedton with triangular faces caped by more argon atoms.[155]

Cu+Ar2 is predicted to be linear. Cu+Ar3 is predicted to be planar T-shaped with an Ar-Cu-Ar angle of 93°. Cu+Ar4 is predicted to be rhombic planar (not square or tetrahedral). For alkali and alkaline earth metals the M+Ar4 cluster is tetrahedral. Cu+Ar5 is predicted to have a rhombic pyramid shape. Cu+Ar6 has a flattened octahedral shape. Cu+Ar7 is much less stable, and the seventh argon atom is outside an inner shell of six argon atoms. This is called capped octahedral. A complete second shell of argon atoms yields Cu+Ar34. Above this number a structural change takes place with an icosahedral arrangement with Cu+Ar55 and Cu+Ar146 having more stability.[156]

With a strontium ion Sr+ from two to eight argon atoms can form clusters. Sr+Ar2 has a triangle shape with C2v symmetry. Sr+Ar3 has a trigonal pyramid shape with C3v symmetry. Sr+Ar4 has two trigonal pyramids sharing a face and strontium at the common apex. It has a C2v symmetry. Sr+Ar6 has a pentagonal pyramid of argon atoms with the strontium atom below the base.[157]

Niobium tetraargide, Nb+Ar4 probably has the argon atoms arranged in a square around the niobium. Similarly for vanadium tetraargide, V+Ar4. The hexaargides, Co+Ar6 and Rh+Ar6 likely have octahedral argon arrangement.[151] Indium monocation forms clusters with multiple argon, with magic numbers at 12, 18, 22, 25, 28, 45 and 54, and 70 argon atoms, which are numbers for icosahedral shapes.[150]

By zapping copper metal with a UV laser in an argon-carbon monoxide mixture, argon tagged copper carbonyl cations are formed. These ions can be studied by observing which wavelengths of infrared radiation cause the molecules to break up. These molecular ions include CuCO+Ar, Cu(CO)2+Ar, Cu(CO)3+Ar, Cu(CO)4+Ar which are respectively disrupted to lose argon, by infrared wavenumbers 2216, 2221, 2205 and 2194 cm−1 respectively. The argon binding energy is respectively 16.3, 1.01, 0.97 and 0.23 kcal/mol. The infrared absorption peak for Cu(CO)3+Ar is 2205 cm−1 compared to 2199 cm−1 for Cu(CO)3+. For Cu(CO)4+Ar the peak is at 2198 cm−1 compared to 2193 for Cu(CO)4+. For Cu(CO)2+Ar the peak is at 2221 cm−1 compared to 2218.3 for argon free, and for CuCO+Ar the peak is at 2216 cm−1 considerably different to 2240.6 cm−1 for CuCO+. Computationally predicted shapes for these molecular ions are linear for CuCO+Ar, slightly bent T-shaped for Cu(CO)2+Ar and a trigonal pyramid with argon at the top and a flat star like copper tricarbonyl forming the base.[158]

Ions studied by argon tagging include the hydrated proton H+(H2O)nAr with n=2 to 5,[159] hydrated 18-crown-6 ether alkali metal ions,[160] hydrated alkali metal ions,[161] transition metal acetylene complexes,[162] protonated ethylene,[163] and IrO4+.[164]

Argon methyl cations, (or methyliumargon) ArxCH3+ are known for n=1 to 8. CH3+ is a Y shape, and when argon atoms are added they go above and below the plane of the Y. If more argon atoms are added they line up with the hydrogen atoms. ΔH0 for ArCH3+ is 11 kcal/mol, and for Ar2CH3+ it is 13.5 kcal/mol (for 2Ar + CH3+).[165]

Boroxyl ring cationic complexes with argon [ArB3O4]+, [ArB3O5]+, [ArB4O6]+ and [ArB5O7]+ were prepared via a laser vaporization at cryogenic temperatures and investigated by infrared gas phase spectroscopy.[3] They were the first large stable gas phase complexes that feature strong dative bonding between argon and boron.

Dications

[edit]

Dications with argon are known for the coinage metals. Known dications include CuArn2+ and AgArn2+ for n=1-8, with a peak occurrence of CuAr42+, or AgAr42+, and AuArn2+ n=3–7. In addition to the four argon atoms, the six argon atoms clusters have enhanced concentration. The stability of the ions with two positive charges is unexpected as the ionization energy of argon is lower than the second ionization energy of the metal atom. So the positive second charge on the metal atom should move to the argon, ionizing it, and then forming a highly repulsive molecule that undergoes a Coulomb explosion. However these molecules appear to be kinetically stable, and to transfer the charge to an argon atom, they have to pass through a higher energy state.[166] The clusters with four argon atoms are expected to be square planar, and those with six, to be octahedral distorted by the Jahn–Teller effect.

Ion Metal first ionization energy
eV
Metal second ionization
eV
binding energy
eV[166]
Dissociation energy
(kJ/mol)
Bond length
(Å)
Cu2+Ar 7.73 20.29 0.439 2.4
Ag2+Ar 7.58 21.5 0.199 2.6
Au2+Ar 9.22 20.5 0.670 2.6

Polyatomic anions

[edit]
Ball-and-stick model of the complex of superelectrophilic anion [B12(CN)11] with Ar. B12 core has nearly icosahedral symmetry. B – pink, C – grey, N – dark blue, Ar – blue.

Examples of anions containing strong bonds with noble gases are extremely rare: generally nucleophilic nature of anions results in their inability to bind to noble gases with their negative electron affinity. However, the 2017 discovery of "superelectrophilic anions",[167] gas phase fragmentation products of closo-dodecaborates, led to the observation of stable anionic compounds containing a boron-noble gas bond with significant degree of covalent interaction. The most reactive superelectrophilic anion [B12(CN)11], fragmentation product of cyanated cluster [B12(CN)12]2-, was reported to bind argon spontaneously at room temperature.[4]

Solid compounds

[edit]

Armand Gautier noticed that rock contained argon (and also nitrogen) that was liberated when the rock was dissolved in acid[168] however how the argon was combined in rock was ignored by the scientific community.[169]

Fullerene solvates

[edit]

Solid buckminsterfullerene has small spaces between the C60 balls. Under 200 MPa pressure and 200 °C heat for 12 hours, argon can be intercalated into the solid to form crystalline Ar1C60. Once this cools down it is stable at standard conditions for months. Argon atoms occupy octahedral interstitial sites. The crystalline lattice size is almost unchanged at room temperature, but is slightly larger than pure C60 below 265 K. However argon does stop the buckyballs spinning below 250 K, a lower temperature than in pure C60.[170]

Solid C70 fullerene will also absorb argon under pressure of 200 MPa and at a temperature of 200 °C. C70·Ar has argon in octahedral sites and has the rock salt structure, with cubic crystals in which the lattice parameter is 15.001 Å. This compares to the pure C70 lattice parameter of 14.964 Å, so the argon forces the crystals to expand slightly. The C70 ellipsoidal balls rotate freely in the solid, they are not locked into position by extra argon atoms filling the holes. Argon gradually escapes over a couple of days when the solid is stored at standard conditions, so that C70·Ar is less stable than C60·Ar. This is likely to be due to the shape and internal rotation allowing channels through which Ar atoms can move.[171]

When fullerenes are dissolved and crystallized from toluene, solids may form with toluene included as part of the crystal. However, if this crystallization is performed under a high pressure argon atmosphere, toluene is not included, being replaced by argon. The argon is then removed from the resultant crystal by heating to produce unsolvated solid fullerene.[172]

Clathrate

[edit]

Argon forms a clathrate with hydroquinone (HOC6H4OH)3•Ar.[173] When crystallised from benzene under a pressure of 20 atmospheres of argon, a well defined structure containing argon results.[174] An argon-phenol clathrate 4C6H5OH•Ar is also known. It has a binding energy of 40 kJ/mol.[169] Other substituted phenols can also crystallise with argon.[173] The argon water clathrate is described in the Aqueous argon section.

Argon difluoride

[edit]

Argon difluoride, ArF2, is predicted to be stable at pressures over 57 GPa. It should be an electrical insulator.[175]

Ne2Ar and Ar2Ne

[edit]

At around 4 K there are two phases where neon and argon are mixed as a solid: Ne2Ar and Ar2Ne.[176] With Kr, solid argon forms a disorganized mixture.[177]

ArH4

[edit]

Under high pressure stoichiometric solids are formed with hydrogen and oxygen: Ar(H2)2 and Ar(O2)3.[178]

Ar(H2)2 crystallises in the hexagonal C14 MgZn2 Laves phase. It is stable to at least 200 GPa, but is predicted to change at 250 GPa to an AlB2 structure. At even higher pressures the hydrogen molecules should break up followed by metallization.[178]

ArO and ArO6

[edit]

Oxygen and argon under pressure at room temperature form several different alloys with different crystal structures. Argon atoms and oxygen molecules are similar in size, so that a greater range of miscibility occurs compared to other gas mixtures. Solid argon can dissolve up to 5% oxygen without changing structure. Below 50% oxygen a hexagonal close packed phase exists. This is stable from about 3GPa to 8.5 GPa. Typical formula is ArO. With more oxygen between 5.5 and 7 GPa, a cubic Pm3n structure exists, but under higher pressure it changes to a I42d space group form. With more than 8.5 GPa these alloys separate to solid argon and ε-oxygen. The cubic structure has a unit cell edge of 5.7828 Å at 6.9 GPa. The representative formula is Ar(O2)3.[179]

ArHe2

[edit]

Using density-functional theory ArHe2 is predicted to exist with the MgCu2 Laves phase structure at high pressures below 13.8 GPa. Above 13.8 GPa it transforms to AlB2 structure.[180]

Ar-TON

[edit]

Under pressure argon inserts into zeolite. Argon has an atomic radius of 1.8 Å, so it can insert into pores if they are big enough. Each unit cell of the TON zeolite can contain up to 5 atoms of argon, compared to 12 of neon. Argon infused TON zeolite (Ar-TON) is more compressible than Ne-TON as the unoccupied pores become elliptical under increased pressure. When Ar-TON is brought to atmospheric pressure, the argon only desorbs slowly, so that some remains in the solid without external pressure for a day.[181]

Nickel argide

[edit]

At 140 GPa and 1500K nickel and argon form an alloy, NiAr.[182] NiAr is stable at room temperature and a pressure as low as 99 GPa. It has a face-centred cubic (fcc) structure. The compound is metallic. Each nickel atom loses 0.2 electrons to an argon atom which is thereby an oxidant. This contrasts with Ni3Xe, in which nickel is the oxidant. The volume of the ArNi compound is 5% less than that of the separate elements at these pressures. If this compound exists in the core of the Earth it could explain why only half the argon-40 that should be produced during the radioactive decay that produces geothermal heating seems to exist on the Earth.[183]

Organoargon chemistry

[edit]

Organoargon chemistry describes the synthesis and properties of chemical compounds containing a carbon to argon chemical bond.

Very few such compounds are known. The reaction of acetylene dications with argon produced HCCAr2+ in 2008.[184] Reaction of the CF2+3 dication with argon produced ArCF2+2: this reaction is unique to argon among the noble gases.[185]

The compound FArCCH has been theoretically studied and is predicted to be stable.[186] FArCCF might also be stable enough to synthesise and detect, but probably not FArCCArF.[187] Calculations in 2015 suggest that FArCCH and FArCH3 are stable, but not FArCN.[188] FArCC should be kinetically stable, as is also expected of the krypton and xenon (but not helium) analogues.[189] HArC4H (for which the krypton analogue is known) and HArC6H have also been predicted as stable.[190] FArCO+ and ClArCO+ should be metastable and might be possible to characterise under cryogenic conditions.[191] Calculations suggest that HArCCF and HCCArF should be stable, and that HNgCCF molecules should be more stable than HNgCCH (Ng = Ar, Kr, Xe); the corresponding krypton species have been experimentally produced, but not the argon species despite an experimental attempt. HCCNgCN and HCCNgNC (Ng = Ar, Kr, Xe) are likewise computed to be stable, but experimental searches for them have failed.[192]

References

[edit]
[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Argon compounds are a rare class of featuring the argon bonded to other elements, challenging the traditional view of argon as chemically inert due to its stable, closed-shell and high . These compounds are typically unstable under ambient conditions and form only under extreme environments, such as cryogenic temperatures in solid matrices or megabar pressures, where argon's 3p orbitals can engage in covalent or ionic interactions, often with highly electronegative elements like or electropositive metals. The landmark discovery of the first stable neutral compound, (HArF), occurred in 2000 through the photolysis of (HF) in a low-temperature solid matrix, yielding a with a covalent H–Ar bond (dissociation energy ~150 kJ/mol) and an ionic Ar···F interaction, with stability up to approximately 27 K before decomposing to HF and . This breakthrough demonstrated argon's capacity for weak but genuine chemical bonding in its , with HArF exhibiting vibrational frequencies consistent with a linear H–Ar–F structure. Subsequent experimental work has identified additional low-temperature compounds, including ArAuF (argon gold fluoride) and ArBeS (argon beryllium sulfide), synthesized via matrix isolation techniques involving laser ablation or deposition in argon-doped matrices at temperatures below 10 K. These species reveal argon's versatility in forming bonds with transition metals (e.g., Au–Ar in ArAuF) and main-group elements (e.g., Be–Ar–S), with confirming their molecular integrity and bond strengths around 40–60 kJ/mol. Under high-pressure conditions, argon exhibits markedly different reactivity, acting as an electronegative oxidant in intermetallic phases such as ArNi, which stabilizes above 140 GPa and 1500 K through electron transfer from nickel to argon's 3p orbitals, potentially explaining argon's sequestration in Earth's core. Similarly, compounds like MgAr and LiAr form above 100–250 GPa, adopting structures where argon accepts electrons to become anionic (Ar⁻), leading to metallic conductivity and, in some cases, superconductivity (e.g., Li₃Ar with a critical temperature of 17.6 K at 120 GPa). These high-pressure findings, predicted and verified via density functional theory and diamond anvil cell experiments, underscore argon's latent chemical potential in geophysical contexts.

Cationic species

Argonium and hydride cations

Argonium, denoted as ArH⁺, is the simplest cationic species involving and , consisting of an atom bonded to a proton. It represents the first confirmed interstellar molecule containing a , with its discovery announced in 2013 through detection of rotational emission lines from the using the Heterodyne Instrument for the Far-Infrared (HIFI) on the . Subsequent observations in 2014 confirmed its presence via toward the Sagittarius B2 star-forming region, establishing ArH⁺ as a tracer of diffuse atomic gas where the molecular fraction is low (approximately 10⁻⁴ to 10⁻³). The formation of ArH⁺ occurs primarily through the reaction of ions with molecular in the gas phase: Ar++H2ArH++H\text{Ar}^{+} + \text{H}_{2} \rightarrow \text{ArH}^{+} + \text{H} This exothermic process has an exothermicity of about 1.6 eV and proceeds efficiently at low temperatures due to the high reactivity of Ar⁺. An alternative pathway is direct : Ar+H+ArH+\text{Ar} + \text{H}^{+} \rightarrow \text{ArH}^{+} with a bond dissociation energy D0D_0 of approximately 3.89 eV (corresponding to the of at 369 kJ/mol). The molecule exhibits a strong Ar-H bond, characterized by a fundamental vibrational ωe\omega_e of 2723 cm⁻¹ and an equilibrium rer_e of 1.286 Å, as determined from emission in discharge sources. Variants of argon hydride cations include polyhydrides such as ArH₂⁺ (n=2) and higher ArHₙ⁺ (n>1), which have been studied theoretically and observed experimentally. ArH₂⁺ forms as an intermediate in the Ar⁺ + H₂ reaction and possesses a linear structure with a of about 0.5 eV relative to Ar⁺ + H₂, exhibiting vibrational frequencies around 1000–3000 cm⁻¹; its stability is lower than ArH⁺ but sufficient for observation in ion traps and mass spectrometers. Higher polyhydrides like ArH₃⁺ show even weaker bonding and are predicted to be metastable, with dissociation pathways leading back to ArH⁺ + H₂. These have been synthesized in settings using ion cyclotron resonance traps and hollow cathode discharges, confirming their ro-vibrational spectra. In astrophysical environments, ArH⁺ is ubiquitous in the diffuse (), where it serves as a diagnostic of nearly purely atomic gas due to its formation in regions with trace H₂ and its destruction by reactions with H₂ in denser clouds. Observations with Herschel reveal column densities ranging from 10⁹ to 10¹² cm⁻² along sightlines toward star-forming regions, with no detection in molecular clouds where H₂ abundance exceeds 10⁻². While prominent in supernova remnants like the , searches in planetary nebulae have yielded tentative detections in UV-irradiated envelopes, highlighting its role in tracing ionized, low-density gas in evolved stellar outflows.

Nitrogen- and oxygen-containing cations

Nitrogen- and oxygen-containing cations represent a class of weakly bound or covalent synthesized under controlled laboratory conditions, such as supersonic expansions and molecular beams, to probe the rare instances of participating in chemical bonding. These cations are characterized primarily through and , revealing interactions ranging from charge-transfer complexes to donor-acceptor bonds. The dinitrogen cation, denoted as [Ar–N₂]⁺, is a linear formed in a supersonic planar plasma. Its spectrum, recorded with a tunable , shows over 70 rovibrational transitions near 2272 cm⁻¹ assigned to the N₂ stretching fundamental in the ²Σ⁺ , shifted from the free N₂⁺ value of 2175 cm⁻¹ due to the interaction with . confirms a linear with the positive charge predominantly localized on the atom, indicating a charge-switch effect upon complexation. The aminargonyl cation ArNH⁺ has been examined theoretically as a covalent , with high-level quartic force field calculations predicting an Ar–N bond strength of approximately half that of ArH⁺ (1.87 mdyne/Ų versus 3.88 mdyne/Ų). Rovibrational analysis provides fundamental vibrational frequencies accurate to within 1 cm⁻¹, aiding potential laboratory detection via , though no experimental observation has been reported to date. Quantum chemical methods suggest viability for synthesis in interstellar or discharge environments analogous to ArH⁺ formation. For oxygen-containing species, the argoxonium cation ArOH⁺ exists in singlet and triplet isomers, both prepared in a cold molecular beam using distinct ion sources. Infrared photodissociation with messenger atom tagging distinguishes the isomers, confirming the singlet ground state as more stable by 3.9 kcal mol⁻¹, featuring a covalent Ar–O donor-acceptor bond with a dissociation energy of 66.4 kcal mol⁻¹ at the CCSD(T)/ level. The triplet state exhibits weaker interaction, while quantum calculations predict equilibrium bond lengths supporting the covalent nature in the singlet form. These findings highlight ArOH⁺ as a rare example of stable argon-oxygen bonding under isolated conditions. Hybrid oxygen-nitrogen species like ArN₂O⁺ remain underexplored, but related complexes such as Ar–HCO⁺ demonstrate weak of the formyl cation HCO⁺ by in gas-phase clusters. In supersonic jet expansions, the first Ar atom binds linearly to the oxygen end of HCO⁺, with subsequent Ar atoms forming a solvation ring; spectra and calculations reveal size-dependent shifts in the C–O stretch, from 2185 cm⁻¹ in bare HCO⁺ to lower values in larger clusters, emphasizing electrostatic and dispersion forces. Mass-selected confirms stability up to n=6 Ar atoms.00217-7) These cations are isolated using low-temperature matrix isolation or supersonic jet techniques to stabilize the fleeting bonds at cryogenic temperatures, preventing rapid dissociation observed in warmer environments. Such methods, combined with high-resolution , provide insights into 's subtle reactivity beyond its inert reputation.

Carbon- and boron-containing cations

The Ar-HCO+^+ cation, also denoted as the -formyl complex, features a weakly bound structure where attaches to the HCO+^+ core primarily through electrostatic and charge-induced dipole interactions. High-resolution has revealed a linear for the ground state, with the Ar atom positioned near the carbon end of HCO+^+, and a of approximately 4.37 kcal/mol calculated at the coupled-cluster level. This complex is metastable and has been observed in gas-phase experiments using pulsed discharge supersonic expansions seeded with , , and carbon monoxide precursors, where HCO+^+ forms via protonation of CO followed by solvation by Ar. Theoretical studies confirm the stability of this T-shaped or linear configuration, with vibrational frequencies matching experimental IR spectra in the 2000–3000 cm1^{-1} region for the C-H stretch. The ArCO2+_2^+ cation represents a weakly bound between Ar+^+ and CO2_2, characterized by charge-transfer and ion-dipole bonding, with the interacting primarily with the oxygen atoms of the linear CO2+_2^+ core. Experimental dissociation energies, measured via threshold photoelectron photoion coincidence , indicate a bond strength of about 0.2–0.3 eV, leading to primary dissociation pathways yielding Ar + CO2+_2^+ or, at higher energies, fragment ions like CO+^+ + O via . Collisional activation studies in further show that ArCO2+_2^+ undergoes symmetric dissociation in collisions with Ar, consistent with a spectator mechanism where the complex acts as a stable intermediate before breakup. Ab initio calculations at the MP4 level support a C2v_{2v} structure, with the dissociation barrier low enough for facile decomposition at room temperature. Ion-molecule reactions involving Ar+^+ and CO proceed primarily via exothermic charge transfer to form CO+^+ + Ar, with a measured rate constant of 4.40×10114.40 \times 10^{-11} cm3^3 s1^{-1} at thermal energies, though transient ArCO+^+ intermediates may form in collision complexes before dissociation. These kinetics highlight the role of such adducts in interstellar chemistry and plasma environments, where ArCO+^+ serves as a short-lived species with a lifetime on the order of vibrational periods. Boron-containing argon cations, such as the Arn_nBO+^+ (n=1–3) clusters, exhibit unusual multiple bonding between and , synthesized in gas-phase reactors using targets in carrier gas with oxygen impurities. of these clusters reveals adiabatic detachment energies increasing with n, from ~8.5 eV for n=1 to ~9.2 eV for n=3, indicating progressive stabilization through shells around the BO+^+ core. The n=1 complex features a linear Ar-BO+^+ geometry with a strong Ar-B σ-bond ( ~20 kcal/mol), while larger clusters form cyclic or bridged structures, as confirmed by DFT and CCSD(T) calculations showing dative bonding from Ar lone pairs to empty B orbitals. These species are highly reactive but persist in ultracold expansions, with theoretical predictions of enhanced stability at low temperatures (<10 K) due to reduced thermal dissociation rates. Theoretical investigations suggest that carbon- and boron-involving argon cations like Ar-HCO+^+ and ArBO+^+ could exhibit increased stability under extreme conditions, such as high pressures (>10 GPa) or cryogenic temperatures, where van der Waals enhancements and reduced favor bound states over dissociation. For instance, coupled-cluster computations predict that compression stabilizes the Ar-B multiple bond in ArBO+^+ by ~5–10 kcal/mol at gigapascal pressures, potentially enabling isolation in matrix or solid-state environments. Similar low-temperature predictions hold for ArCO2+_2^+, with dissociation barriers rising due to confinement effects in dense media.

Metal-involving cluster cations

Metal-involving cluster cations refer to positively charged species where argon atoms solvate or coordinate with metal ions or small metal clusters, typically formed in the gas phase through techniques like followed by supersonic expansion and ionization. These clusters are studied primarily using time-of-flight (TOF) , which allows for size selection and analysis of stability based on abundance intensities in mass spectra. Pure argon cluster cations, Ar_n^+, serve as precursors for metal-doped variants, exhibiting core structures like Ar_3^+ with enhanced stability due to a sudden drop in binding energy increments between n=3 and n=4. However, high-resolution mass spectrometry reveals that apparent magic numbers in Ar_n^+ distributions (e.g., n=13, 19, 55) often arise from unresolved protonated Ar_n H^+ impurities rather than intrinsic stability of pure cationic clusters, which lack pronounced icosahedral shell closures. In contrast, when transition metals are introduced, such as in Ti^+ Ar_n clusters produced by laser vaporization of titanium in an argon expansion, distinct magic numbers emerge; for instance, Ti^+ Ar_6 shows exceptional abundance, corresponding to a completed octahedral first coordination shell around the metal cation. Similarly, Ni^+ Ar_n and Pt^+ Ar_n clusters display pronounced intensities at n=4 and n=6, indicative of stable solvation shells influenced by the d^9 electronic configuration of these metals. For coinage metals like and , argon solvation perturbs the cluster geometry and electronic structure. In Cu_n^+ (n=1–10) clusters generated via and tagged with argon for infrared multiple photon dissociation (IRMPD) , sequential Ar attachment leads to fragmentation patterns dominated by loss of Ar atoms, with binding energies decreasing after the first Ar due to charge redistribution. Computational modeling using (DFT) with dispersion corrections reveals that bonding is predominantly electrostatic and dispersion-dominated, augmented by ~0.08 e charge transfer from Ar to Cu, introducing partial covalent character that weakens subsequent Ar bindings. Analogously, Au_n^+ (n=3–20) clusters adsorb up to six Ar atoms on smaller sizes (n≤7), with Au_15^+ exhibiting uniquely strong binding (~0.3 eV adsorption energy) at a low-coordinated site, as confirmed by TOF mass spectra and PBE+D3/ECP DFT calculations showing electron donation from Ar to Au, forming a partial . These examples highlight how metal identity modulates fragmentation, with smaller clusters favoring higher Ar coordination before evaporative loss in the TOF analyzer. Overall, bonding in these blends ion-induced with minor covalent contributions via charge transfer, as modeled by DFT, which predicts shells completing at coordination numbers like 6 for octahedral preferences in early transition metals. Experimental fragmentation via IRMPD or collisions reveals stepwise Ar loss, providing insights into energies without significant metal-Ar bond breaking.

Anionic and dicationic species

Polyatomic anions

Polyatomic anions containing represent a class of highly unstable, noble gas-involved that challenge the traditional inertness of due to its closed-shell electronic configuration and negative atomic . These anions, such as electron-attached clusters Ar_n^- (where n ≥ 2) and mixed-ligand examples like ArF^- and ArOH^-, feature weak interactions ranging from van der Waals complexes to partial covalent bonding in select cases. Observed exclusively in controlled environments, they exhibit no significant natural occurrence, with synthesis confined to gas-phase techniques that exploit low-temperature conditions or high-energy processes to overcome thermodynamic barriers. Formation of these anions typically occurs via electron attachment to neutral argon clusters or pre-formed complexes in crossed-beam experiments, where low-energy s (often from electron guns or collisions) interact with supersonic expansions of or argon-doped mixtures. For instance, Ar_n^- clusters form through sequential of an excess electron onto neutral Ar_n, stabilized momentarily by the polarizable environment of the cluster before potential autodetachment. Mixed anions like ArF^- arise from associative attachment involving ions and argon atoms, as evidenced by mass spectrometric detection in ion trap or flow tube reactors. Similarly, ArOH^- can be generated from reactions of precursors with argon in discharge sources or matrix isolation setups, though yields remain low due to competing dissociation channels. These methods highlight the transient nature of the species, with detection relying on sensitive techniques like . Stability assessments reveal short autodetachment lifetimes for many of these anions, often on the order of microseconds to milliseconds, driven by the excess 's tendency to escape the shallow formed by the cluster's induced . Photoelectron provides key insights, showing broad detachment thresholds that indicate vibrational relaxation and formation; for Ar_n^-, spectra display progressive shifts in with increasing n, reflecting enhanced stabilization from subsurface electron states in larger clusters. ArF^-, for example, exhibits a modest of 8.37 kJ/mol, underscoring its weakly bound character, while ArOH^- shows slightly stronger interactions due to partial transfer from the electronegative OH group. Theoretical calculations, primarily at the coupled-cluster level (e.g., CCSD(T)), predict orbital energies where the excess occupies diffuse, Rydberg-like orbitals delocalized over the framework, with effects from additional Ar atoms lowering the detachment threshold by up to 0.1-0.2 eV per solvent molecule through polarization enhancement. These computations also reveal modest covalent contributions in oxygen-involved species like ArOH^-, where Ar-O arises from donation into antibonding orbitals, though overall barriers to dissociation remain low (typically <10 kcal/mol). Such findings emphasize the role of environmental stabilization in extending lifetimes, yet confirm these anions' confinement to exotic, non-equilibrium conditions.

Dications

Argon dications, such as Ar22+_2^{2+} and higher-order Arn2+_n^{2+} (n > 2), are transient species primarily studied in the gas phase due to their instability arising from strong Coulomb repulsion between the positively charged centers. These dications are generated through double ionization processes, often using synchrotron radiation to excite and remove two electrons from argon dimers or clusters in a controlled manner. For instance, core photoionization experiments in the 255–340 eV range have revealed multiple ionization pathways leading to Ar22+_2^{2+}, highlighting the role of interatomic electron correlations in the dimer. The ground state of Ar22+_2^{2+} (1Σg+^1\Sigma_g^+) is quasi-bound, featuring a shallow potential well with an equilibrium bond length of 3.87 bohr, as determined by configuration interaction ab initio calculations. This shallow well results from a delicate balance between attractive exchange forces and dominant Coulomb repulsion, leading to short lifetimes for vibrational states in the well. Higher-order Arn2+_n^{2+} dications exhibit greater stability for larger n, with the smallest observable size being n = 73 in helium nanodroplet experiments, where evaporation and fission compete with detection timescales of about 50 µs. Reactivity of these dications is dominated by rapid fragmentation via Coulomb explosion, typically yielding Ar+^+ + Ar+^+ pairs from Ar22+_2^{2+}, with kinetic energy releases (KER) around 3.8–5.2 eV depending on the relaxation pathway—such as interatomic Coulombic decay (ICD) or radiative charge transfer (RCT). In ICD, energy from one ionized site ejects an electron from the neighboring atom on femtosecond timescales (~100 fs for fast channels), while RCT involves photon emission over nanosecond scales. These processes underscore the dications' role in energy dissipation in rare-gas systems, analogous to mechanisms in larger clusters. Charge transfer reactions further contribute to dissociation, with potential energy surfaces indicating barriers that favor fragmentation over stable bonding. In comparison, the helium analog He22+_2^{2+} features a more stable with a deeper well (~2.5 eV) and shorter (~1.08 Å), allowing experimental detection and manipulation in radiofrequency ion traps at low energies (<1 eV) for studies of charge transfer dynamics. Unlike Ar22+_2^{2+}, which lacks sufficient binding for such trapping due to enhanced repulsion in heavier rare gases, He22+_2^{2+} serves as a benchmark for understanding charge-induced bonding in diatomic dications.

Neutral molecular species

Van der Waals molecules

Van der Waals molecules involving consist of weakly bound aggregates where the primary interactions are dispersion forces arising from instantaneous dipole fluctuations between atoms or molecules. These forces dominate due to argon's closed-shell electronic structure and low , resulting in shallow wells and large equilibrium separations typically around 3.5–4.5 , governed by the of at 1.88 . Unlike covalent bonds, these interactions are non-directional and sensitive to quantum effects like , often leading to floppy structures observable via high-resolution . Argon clusters, denoted as Ar_n for n ≥ 2, form readily in supersonic expansions of argon gas through adiabatic cooling and , where high stagnation pressures (10–100 bar) and nozzle temperatures (200–300 ) control the mean cluster size from small oligomers to thousands of atoms. The thermodynamic properties include stepwise binding energies that decrease with increasing n, reflecting surface and bulk contributions; for example, the Ar_2 dimer has a dissociation energy of 99.4 cm⁻¹ and equilibrium distance of 3.76 , while larger clusters exhibit evaporative cooling and melting-like transitions around 20–40 . These clusters serve as model systems for studying phase behavior in finite systems, with formation dynamics modeled by accounting for three-body collisions during expansion. Diatomic complexes like Ar–He feature extremely weak binding, with a potential well depth of approximately 0.02 cm⁻¹ and equilibrium separation exceeding 7 Å, due to helium's minimal polarizability limiting dispersion. The Ar–Ne dimer binds more strongly at about 25 cm⁻¹ with a 3.65 Å distance, enabling observation of vibrational levels. Mixed species such as Ar_2Ne and Ne_2Ar exhibit asymmetric potentials, with ab initio calculations revealing T-shaped minima influenced by steric effects and exchange repulsion. Triatomic complexes, including Ar–He_2 and Ar_2–He (or ArHe_2), display both linear and cyclic isomers, with linear forms generally more stable owing to reduced Pauli repulsion; for instance, in analogous rare-gas trimers, the linear Ar–He–Ar configuration has a around 0.05 cm⁻¹, while cyclic variants are higher in energy by 10–20%. of mixed rare-gas trimers confirms floppy rotations and tunneling between isomers, highlighting the role of anisotropic dispersion in stabilizing these structures. Polyatomic complexes like Ar–H_2 adopt a T-shaped equilibrium with the above the H–H bond midpoint, bound by 41 cm⁻¹, as determined from high-resolution and spectra revealing rotational constants and centrifugal distortion. The intermolecular potential is anisotropic, with leading C_6 dispersion term of 65 a.u., and zero-point effects elongate the structure. For Ar–N_2, identifies a T-shaped minimum with 110 cm⁻¹ dissociation energy and ^{14}N coupling constants indicating nearly free rotation of N_2, underscoring combined dispersion and contributions to the potential.

Covalent and polar molecules

Neutral argon molecules exhibiting partial covalent character are exceedingly rare due to argon's high and low electronegativity difference with most elements, rendering such bonds unstable under standard conditions. These species are primarily studied through theoretical computations or transient isolation in matrices at cryogenic temperatures (typically 4–20 K), where they can be generated via photolysis or deposition techniques before rapid decay. Unlike purely van der Waals complexes, these molecules feature significant orbital overlap, leading to polar or covalent bonding contributions, often analyzed through models involving charge transfer or hypervalent structures. Experimentally observed examples include (HArF) and compounds like ArAuF and ArBeS, synthesized in low-temperature matrices, demonstrating argon's ability to form weak covalent bonds. Argon difluoride (ArF₂) represents a prototypical example of a theoretically predicted covalent compound, characterized by a linear or nearly linear F–Ar–F geometry. calculations at the coupled-cluster level predict an Ar–F of approximately 1.76 for the free , with a dissociation energy barrier of about 2.95 eV relative to Ar + 2F atoms, indicating metastable stability but high reactivity. Although attempts to isolate ArF₂ in matrices have not succeeded due to its instability, theoretical vibrational frequencies suggest Raman-active symmetric stretching modes around 600–700 cm⁻¹, providing potential spectroscopic signatures if stabilized. The decomposes primarily via dissociation to Ar + F₂ or 2F + Ar, with no measurable in ambient conditions but predicted lifetimes on the order of picoseconds in gas phase based on energy barriers. Other transient neutral species, such as monoxide (ArO), have been synthesized in argon matrices through photolysis of O₂-doped matrices or reactions involving atomic oxygen. ArO exhibits excimer-like behavior in the matrix, with emission spectra peaking around 558 nm, attributed to bound excited states decaying to repulsive ground states. The radiative lifetime of ArO emission in argon matrices is measured at approximately 10–20 ns, with non-radiative decay pathways dominating via energy transfer to the matrix host. Theoretical studies of larger species like ArO₆ (proposed as Ar(O₂)₃) predict a structure with argon coordinated to three units, featuring polar Ar–O interactions with bond lengths around 2.0–2.2 and transfer from oxygen lone pairs to argon's empty orbitals. Such configurations are metastable in computations, with binding energies of 0.5–1.0 eV per Ar–O link, but no matrix isolation has been reported due to barriers below 1 eV; predicted UV-Vis absorptions lie in the 200–250 nm range from charge-transfer transitions. Bonding in these species contrasts hypervalent models (e.g., three-center four-electron bonds in ArF₂, emphasizing d-orbital participation) with charge-transfer frameworks (e.g., in ArO, where excitation promotes electron donation from O to Ar, stabilizing the bond transiently).

Solution and aqueous chemistry

Aqueous argon

Argon exhibits low in , behaving as a non-reactive that dissolves primarily through physical interactions governed by . The Henry's law constant for argon in water at 298.15 K is 0.0014 mol kg⁻¹ bar⁻¹, corresponding to a of approximately 1.4 mmol L⁻¹ at 1 bar partial . This decreases with increasing , as described by the van't Hoff relation with a dependence parameter d(ln k_H)/d(1/T) of approximately 1500 K, reflecting an exothermic process with an of solution around -12 kJ mol⁻¹. Measurements confirm this trend, with dropping from about 2.5 mmol L⁻¹ at 0°C to 1.0 mmol L⁻¹ at 40°C under standard conditions. The hydration structure of argon in dilute aqueous solutions has been characterized using neutron diffraction, revealing a hydrophobic solvation shell. The partial radial distribution function g_ArO(r) shows a primary peak at 3.40 , indicating the position of oxygen atoms in the first hydration shell, with a coordination number of approximately 5.5 molecules. The Ar-H distribution peaks at around 4.3 , consistent with hydrogen atoms oriented outward from the oxygen lone pairs facing the atom. This arrangement enhances local water structuring, forming transient clathrate-like cages around the atom without covalent bonding, as evidenced by simulations that align with experimental data. No stable chemical compounds form under ambient conditions, underscoring 's inertness in aqueous media. Despite efforts, no stable argon compounds have been synthesized in aqueous solutions, even under extreme conditions like or with strong oxidants, due to argon's high and stable . In biological contexts, argon's solubility and weak interactions have implications for diving physiology, where it acts as an inert gas capable of inducing narcosis. When breathed under hyperbaric conditions, argon produces inert gas narcosis more potently than , with anesthetic effects onsetting at lower partial pressures due to its higher solubility and ability to modulate neuronal channels. This narcotizing effect, observed in animal models and studies, limits argon's use in diving mixtures, as it impairs cognitive function and at depths beyond 20 m. Isotopic variations in argon solubility arise from subtle differences in mass-dependent interactions with water. The solubility fractionation factor α for the ⁴⁰Ar/³⁶Ar ratio is approximately 1.0045 at 25°C, indicating that heavier isotopes are slightly more soluble, leading to enrichment of lighter isotopes in the gas phase during equilibration. These effects, quantified through precise laboratory measurements, are small but significant for geochemical applications, such as tracing ocean ventilation and paleotemperature reconstruction using dissolved noble gases. Temperature influences the fractionation, with α decreasing slightly from 1.005 at 2°C to 1.004 at 20°C.

Solid-state compounds

Binary and simple solids

Binary and simple solids of are typically formed under cryogenic conditions or high pressures, where weak intermolecular forces or induced chemical bonding stabilize the structures. These compounds include van der Waals adducts and predicted covalent species, synthesized primarily through condensation of gaseous mixtures onto cold surfaces or by compressing mixtures in diamond anvil cells. difluoride (ArF₂) in solid form is predicted to be thermodynamically stable above approximately 60 GPa, adopting a layered molecular with ArF₂ units separated by unbound atoms. Computational studies using indicate that this polymorph consists of three-atom-thick layers of interspersed with monolayers of ArF₂ molecules, with Ar-F bond lengths around 1.76 Å at , shortening under compression. Such high-pressure stabilization arises from the balance between argon-fluorine bonding and lattice packing, though experimental synthesis remains challenging due to the extreme conditions required. Solid ArH₄, equivalently notated as Ar(H₂)₂, forms as a weakly bound van der Waals compound where two molecules occupy interstitial sites in an lattice, exhibiting a Laves-phase analogous to MgZn₂. diffraction experiments on compressed Ar-H₂ mixtures up to 46 GPa at confirm its stability, revealing a cubic with lattice parameter a ≈ 5.31 Å at low pressures, transitioning under further compression without dissociation up to 358 GPa in theoretical models. This compound highlights argon's role as a "" stabilizing dense phases, with no metallization observed below 100 GPa. ArHe₂, or Ar(He)₂, represents a weakly bound solid where helium atoms interact via van der Waals forces with central argon, stable at low pressures in a Laves MgCu₂-type phase before transitioning to an AlB₂ structure above 10 GPa. First-principles calculations predict its vibrational properties, including low-frequency modes indicative of weak bonding, with the solid persisting up to high pressures without decomposition.

Complex and polyatomic solids

Complex and polyatomic solids involving argon often feature the noble gas incorporated into lattices with multiple atomic species, stabilized by high pressure or specific host structures. One notable example is the formation of argon-oxygen alloys under high pressure at room temperature. These include ArO₂ and Ar₃O₂, embedded in oxygen-rich matrices. These phases exhibit distinct crystal structures, such as body-centered tetragonal for ArO₂ and more complex arrangements for Ar₃O₂, demonstrating argon's ability to form polyatomic solids beyond simple binaries when electronegativity differences are altered under compression. Intermetallic compounds like argide (NiAr) represent another class of complex solids synthesized via high-pressure techniques. NiAr forms a (MgZn₂-type structure) at pressures above 100 GPa and temperatures exceeding 2000 K, achieved using diamond anvil cells with heating on - mixtures. This compound remains metastable down to 99 GPa at , with atoms occupying interstitial sites in the lattice, suggesting potential relevance to sequestration in planetary cores. Characterization via confirms the cubic structure with lattice parameter a ≈ 4.95 Å, highlighting the that stabilizes the polyatomic framework. Argon incorporation into titanosilicate frameworks, such as in ETS-10 molecular sieves, creates complex solids where adsorbs at specific cationic sites. In silver-exchanged ETS-10 (Ag-ETS-10), preferentially interacts with Ag⁺ ions within the microporous titanosilicate structure, exhibiting higher adsorption capacity and selectivity over oxygen and due to π-backbonding interactions (Ar pσ–Ag dσ). Adsorption sites are located near the titanium-centered tetrahedra and extra-framework cations, with isosteric heats around 15–20 kJ/mol, enabling efficient gas separation in polyatomic host lattices. These frameworks provide ordered adsorption environments, contrasting simpler solids by integrating into extended networks. Fullerene solvates, particularly , exemplify polyatomic solids where is trapped within the C₆₀ cage. Synthesized by high-pressure high-temperature treatment of C₆₀ soot in (up to 0.5 GPa, 800°C) or via molecular (cage opening, Ar insertion, and closure), these compounds feature a single Ar atom encapsulated in the icosahedral , confirmed by and NMR. Release kinetics follow an Arrhenius process with ≈80 kcal/mol, occurring via temporary cage distortion (window mechanism) at elevated temperatures above 1000 K, allowing controlled desorption while maintaining integrity. Vibrational modes in these complex argon solids are probed using , providing insights into bonding and dynamics. For Ar@C₆₀, Raman spectra reveal blue-shifted low-energy modes (e.g., Ag(1) at 273 cm⁻¹ shifting to 274 cm⁻¹) due to Ar-induced cage stiffening, with the exhibiting rattling motions inside the cavity. In NiAr Laves phases, Raman analysis of modes confirms lattice stability, showing characteristic intermetallic vibrations around 200–400 cm⁻¹. Similarly, argon-oxygen alloys display Raman-active O–Ar stretches in the 800–1000 cm⁻¹ region, distinguishing polyatomic interactions from matrix-isolated species. These spectroscopic signatures enable precise characterization of argon's role in multifaceted solid-state environments.

Clathrates and intercalation compounds

Argon clathrate hydrates consist of atoms encapsulated within cage-like polyhedra formed by hydrogen-bonded molecules, forming a crystalline inclusion compound distinct from pure ice Ih. At and temperatures below 273 K, argon stabilizes the cubic structure II () clathrate, which features a of 136 molecules enclosing 16 small pentagonal dodecahedral (5^{12}) cages and 8 larger hexakaidecahedral (5^{12}) cages. In this , the small cages exhibit near-complete (≈1.0) by single argon atoms, while the large cages show partial (≈0.6 under equilibrium conditions at typical formation pressures of 20–50 bar), resulting in an overall of approximately Ar·6.5H₂O. These hydrates form through the freezing of aqueous argon solutions under elevated argon pressure, typically 10–60 bar, where dissolved argon (from prior equilibration in the aqueous phase) nucleates within the forming ice lattice during cooling to 250–270 K. The process favors heterogeneous nucleation at ice-water interfaces, with induction times decreasing as pressure increases due to higher argon solubility and driving force for cage filling. Under compression, clathrate hydrates undergo pressure-induced phase transitions that alter the host framework to optimize packing and argon occupancy. The sII phase remains stable up to ≈4.6 kbar at 100–150 K, transitioning to hexagonal structure III () with a stoichiometry of ·3.4H₂O and fuller large- occupancy (up to 5 argon atoms per via multiple occupation); further pressurization to ≈7.7 kbar yields tetragonal structure IV (sT, ·3H₂O), featuring a single polyhedral type with double argon occupancy. These transitions, observed via neutron diffraction, reflect increasing distortion and argon filling efficiency, with the phase exhibiting enhanced stability up to 10 kbar before potential amorphization. Beyond hydrates, forms intercalation compounds in microporous frameworks like s, where it physisorbs within intracrystalline channels acting as host cages. In 4A, argon follows an activated mechanism, with intracrystalline coefficients ranging from 10^{-8} to 10^{-7} cm²/s at 298 K and low loadings, influenced by pore size and electrostatic fields from framework cations. Similar behavior occurs in MFI-type s, where argon loading affects transport, with self- coefficients decreasing at higher occupancies due to site-blocking effects. Intercalation in layered materials like is less common for argon owing to its inert nature and weak interactions, but studies indicate limited penetration between sheets under cryogenic or high-pressure conditions. Due to their cage-trapping efficiency and thermal stability, argon clathrates and zeolite intercalates offer potential for gas storage applications, enabling reversible encapsulation at moderate pressures (10–100 bar) with slow guest (rates <10^{-12} /s at 200 ) ensuring long-term retention. These properties position them as models for sequestration, though practical use focuses more on scalable analogs like hydrates.

Metal and organoargon compounds

Transition and coinage metal compounds

Coinage metal monohalides such as ArAgCl have been synthesized and characterized using pulsed-jet . These complexes are produced by co-deposition of laser-ablated silver atoms with halogen-containing precursors in a supersonic expansion of carrier gas, allowing isolation of the transient species at low temperatures. The structure of ArAgCl is linear (Ar-Ag-Cl), with an Ar-Ag of 2.60 and a estimated at approximately 23 kJ/mol, indicating a weak but rigid interaction primarily involving charge transfer from the to the silver-halide antibonding orbital. Similar complexes, including ArAgF and ArCuF, exhibit comparable bonding motifs, with Ar-M s ranging from 2.25 for ArCu to 2.60 for ArAg, as determined by and supported by DFT calculations at the B3LYP level using aug-cc-pVTZ basis sets. Transition metal oxides form weakly bound complexes with argon in noble gas matrices, exemplified by ArFeO and ArNiO. These species are generated via co-deposition of laser-ablated iron or atoms with O2 in excess at 4-10 K, followed by matrix isolation to observe characteristic vibrational shifts. For ArFeO and ArNiO, the coordination results in linear Ar-M-O structures, where binds to the metal center opposite the oxygen ; DFT calculations (B3LYP/6-311++G(3df,3pd)) predict Ar-M bond lengths of approximately 2.8-3.0 Å and binding energies increasing from ~2 kcal/mol for ArFeO to ~4 kcal/mol for ArNiO, reflecting enhanced d-orbital overlap with later s. spectra show small red shifts in the M-O stretching frequency (e.g., 10-20 cm⁻¹ for ArNiO at ~850 cm⁻¹), attributable to weak σ-donation from Ar to empty metal d-orbitals. Carbonyl compounds of the form ArM(CO)_n (M = Ni, Cu, Ag; n = 1-2) are isolated in matrices through co-deposition of laser-ablated metal atoms with CO, enabling observation of substitution where acts as a transient to coordinatively unsaturated sites. DFT studies (BP86/def2-TZVP) indicate that coordination to M(CO) involves dative via metal d-orbitals, with Ar-M distances ~2.5-3.0 and dissociation energies ~3-5 kcal/mol, facilitating stepwise CO addition or replacement in the matrix environment. These interactions highlight argon's role in stabilizing low-coordinate intermediates, analogous to ionic cluster cations like ArM^+ (M = Fe, Ni) observed in , where electrostatic is stronger (~10-20 kcal/mol). Bonding in these argon-transition and coinage metal compounds is characterized by weak covalent interactions, with significant involvement of metal d-orbitals as revealed by DFT analyses (e.g., MP2 and CCSD(T) methods). For instance, in ArAgCl, analysis shows ~0.1 e charge transfer from Ar to Ag, populating Ag 5s/5p and d-hybrids, while in ArNiO, the Ar-Ni bond features σ-donation to Ni 3d_{z^2} orbital, enhancing stability through partial back-donation. These calculations, benchmarked against experimental vibrational and rotational data, confirm the hybrid dispersion-covalent nature of the bonds, with d-orbital contributions scaling with metal and .

Uranium and beryllium compounds

Argon forms weak bonds with in matrix-isolated complexes, particularly through interactions with the uranium atom in species like CUO. In solid matrices at 4 K, laser-ablated atoms react with to produce CUO, which coordinates multiple atoms, resulting in complexes such as CUOAr and CUOAr_n (n up to 5), evidenced by shifts in the CUO stretching frequencies from U-C ~1047 cm⁻¹ and U-O ~872 cm⁻¹ in to U-O ~852 cm⁻¹ and U-C ~804 cm⁻¹ in . These bonds arise from polarization and partial charge transfer from to the electron-deficient center, with theoretical calculations indicating binding energies of approximately 3-5 kcal/mol per U-Ar interaction. In uranium pnictide chemistry, serves as an inert matrix for isolating reactive species, such as the uranimine nitride N≡U–NH, prepared by codeposition of laser-ablated atoms with in solid at low temperatures. This compound exhibits a characteristic N≡U stretch at 987.3 cm⁻¹, confirming the terminal uranium-nitrogen stabilized within the host, which prevents further reaction. High-pressure studies of pnictides, such as UN, often employ as a hydrostatic pressure-transmitting medium to explore phase stability up to several GPa, maintaining sample integrity without chemical interference. Beryllium oxide interacts with argon to form the weakly bound ArBeO complex, characterized by a collinear Ar–Be–O structure where argon coordinates to the electron-deficient beryllium atom. Theoretical calculations at the MP2 level predict a dissociation energy of 4.0 kcal/mol for ArBeO, significantly stronger than analogous HeBeO (0.8 kcal/mol) or NeBeO (1.5 kcal/mol), due to enhanced electrostatic and induction contributions from argon's . This complex is synthesized via of beryllium metal in the presence of oxygen diluted in excess argon at 10 , yielding infrared absorptions shifted from free BeO, indicative of matrix perturbation and weak . Electronic properties of these argon-involved compounds reveal subtle charge transfer effects, as seen in theoretical studies of uranium oxides in noble gas matrices, where the uranium 5f orbital configuration shifts from 5f¹7s¹ in neon to 5f² in argon, reflecting increased electron donation from the host gas. Theoretical investigations predict potential superconductivity in compressed uranium systems under high pressure, where argon acts as a non-reactive medium; for instance, uranium polyhydrides like UH₇ exhibit calculated T_c values up to 54 K at 20 GPa, though direct U-Ar phases remain unexplored for such properties.

Organoargon chemistry

Organoargon chemistry involves the formation of direct argon-carbon (Ar-C) bonds, which are exceptionally rare owing to argon's chemical inertness and preference for weak van der Waals interactions over covalent bonding. Unlike more common organometallic compounds, organoargon species typically exist only as short-lived cations or theoretically predicted neutrals, often requiring extreme conditions such as gas-phase reactions or cryogenic matrix isolation for detection or stabilization. Early theoretical work in the highlighted the potential for such bonds, but no stable, isolable organoargon compounds have been reported to date. A seminal experimental example is the gas-phase synthesis of the cation ArCH₂⁺, achieved in through the bimolecular reaction of mass-selected CH₂BrH₂²⁺ dications with neutral atoms. This species, detected via , represents a novel class of organo rare-gas cations with a chemically bound Ar-C linkage, where the acts as a center. The Ar-C bond in ArCH₂⁺ is notably strong, exceeding the dissociation energy of the related ArOH⁺ cation, enabling its observation despite the general instability of compounds. Theoretical predictions have further expanded the scope of potential organoargon species. In 2003, calculations identified FArCCH as a metastable neutral featuring an Ar-C bond, protected by a dissociation barrier of approximately 5 kcal/mol, though its fleeting nature prevents room-temperature persistence. Subsequent computational studies in 2006 explored equilibrium structures for HArC₄H, predicting an Ar-C of about 2.183 and vibrational frequencies consistent with weak covalent character, suggesting possible synthesis via photolysis or high-energy activation in matrices. These models indicate that organoargon neutrals decompose rapidly upon warming, with lifetimes under cryogenic conditions but sub-second half-lives in warmer environments. Neutral radicals with Ar-C bonds, such as those potentially formed via photolysis of alkyl halides in matrices, remain largely theoretical, with no confirmed experimental isolation. Computational scans for systems like Ar-phenyl linkages reveal shallow minima indicative of transient bonding, but experimental efforts in the early yielded only weakly bound complexes rather than true covalent species. Overall, organoargon chemistry underscores the limits of reactivity, with ongoing research focusing on superelectrophilic reagents and advanced to probe these elusive bonds.

References

Add your contribution
Related Hubs
User Avatar
No comments yet.