Hubbry Logo
HartreeHartreeMain
Open search
Hartree
Community hub
Hartree
logo
7 pages, 0 posts
0 subscribers
Be the first to start a discussion here.
Be the first to start a discussion here.
Hartree
Hartree
Hartree
View on Wikipedia
from Wikipedia

The hartree (symbol: Eh), also known as the Hartree energy, is the unit of energy in the atomic units system, named after the British physicist Douglas Hartree. Its CODATA recommended value is Eh = 4.3597447222060(48)×10−18 J‍[1] = 27.211386245981(30) eV.[2] The name "hartree" was suggested for this unit of energy.[3][4]

The hartree is approximately the negative electric potential energy of the electron in a hydrogen atom in its ground state and, by the virial theorem, approximately twice its ionization energy; the relationships are not exact because of the finite mass of the nucleus of the hydrogen atom and relativistic corrections.

The hartree is usually used as a unit of energy in atomic physics and computational chemistry: for experimental measurements at the atomic scale, the electronvolt (eV) or the reciprocal centimetre (cm−1) are much more widely used.

Other relationships

[edit]
= 2 Ry = 2 R∞hc
= 27.211386245981(30) eV‍[2]
= 4.3597447222060(48)×10−18 J‍[1]
= 4.3597447222060(48)×10−11 erg
≘ 2625.4996394799(50) kJ/mol
≘ 627.5094740631(12) kcal/mol
≘ 219474.63136320(43) cm−1
≘ 6579.683920502(13) THz

where:

Effective hartree units are used in semiconductor physics where is replaced by and is the static dielectric constant. Also, the electron mass is replaced by the effective band mass . The effective hartree in semiconductors becomes small enough to be measured in millielectronvolts (meV).[5]

References

[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia

Hartree

View on Grokipedia
from Grokipedia
The hartree (symbol: E_h), also known as the Hartree energy, is the atomic unit of energy. It is defined as the absolute value of the ground-state energy of the hydrogen atom, [ E_h = \frac{\hbar^2}{m_e a_0^2} = \frac{e^2}{4 \pi \epsilon_0 a_0} ] where \hbar is the reduced Planck constant, m_e is the electron mass, a_0 is the Bohr radius, e is the elementary charge, and \epsilon_0 is the vacuum permittivity. This corresponds to approximately 4.359744722 \times 10^{-18} J or 27.21138602 eV (2018 CODATA values). The unit is named after the English physicist and mathematician (1897–1958), who made significant contributions to and early .

Definition

Role in atomic units

In the atomic unit system, commonly employed in non-relativistic for atomic and molecular calculations, the reduced Planck's constant ħ, the e, and the m_e are set to unity (ħ = e = m_e = 1). This choice defines a natural scale for physical quantities, with the hartree (E_h) emerging as the fundamental unit of energy derived directly from these constants. The system also includes the a_0 as the unit of length, the m_e as the unit of mass, and the e as the unit of charge, providing a cohesive framework that eliminates explicit constants in many equations. The hartree energy is explicitly derived as E_h = \frac{\hbar^2}{m_e a_0^2}, where a_0 represents the , the characteristic length scale in the . This expression arises from balancing the kinetic and potential terms in the under the atomic unit conventions, yielding a consistent energy scale tied to the electron's dynamics near the nucleus. By adopting the hartree as the energy unit, equations in non-relativistic are greatly simplified, as fundamental constants like ħ, m_e, and e disappear from the Hamiltonian and related operators. For instance, the time-independent for a reduces to a dimensionless form, facilitating analytical solutions and numerical computations without dimensional overhead. This systemic role underscores the hartree's utility in establishing the energy benchmark equivalent to twice the of the .

Formal definition

The hartree energy, denoted EhE_\mathrm{h}, is the atomic unit of in the Hartree atomic unit , with its 2022 CODATA recommended value given by Eh=4.359 744 722 2060(48)×10−18E_\mathrm{h} = 4.359\,744\,722\,2060(48) \times 10^{-18} J. This value results from a of fundamental physical constants and auxiliary quantities. Formally, EhE_\mathrm{h} is expressed in terms of fundamental constants as Eh=[e](/page/Elementarycharge)24πϵ0[a0](/page/Bohrradius)E_\mathrm{h} = \frac{[e](/page/Elementary_charge)^2}{4\pi\epsilon_0 [a_0](/page/Bohr_radius)}, where ee is the , ϵ0\epsilon_0 is the , and a0a_0 is the Bohr radius defined by a0=4πϵ0ℏ2me[e](/page/Elementarycharge)2a_0 = \frac{4\pi\epsilon_0 \hbar^2}{m_e [e](/page/Elementary_charge)^2}, with mem_e the and ℏ\hbar the reduced . Substituting the expression for a0a_0 yields the equivalent form Eh=[me](/page/Electronmass)[e](/page/Elementarycharge)4(4πϵ0)2ℏ2E_\mathrm{h} = \frac{[m_e](/page/Electron_mass) [e](/page/Elementary_charge)^4}{(4\pi\epsilon_0)^2 \hbar^2}. Following the 2019 revision of the SI, which fixed the numerical values of ee, hh (hence ℏ\hbar), and the speed of light cc, the uncertainty in EhE_\mathrm{h} arises primarily from measurements of mem_e and the fine-structure constant α\alpha (since Eh=α2mec2E_\mathrm{h} = \alpha^2 m_e c^2). The relative standard uncertainty of 1.1×10−91.1 \times 10^{-9} in the 2022 CODATA value reflects these measurement precisions in the global adjustment. An operational definition ties EhE_\mathrm{h} to spectroscopic data via the Rydberg constant: Eh=2hcR∞E_\mathrm{h} = 2 h c R_\infty, where R∞R_\infty is the Rydberg constant for infinite nuclear mass. This relation connects the atomic unit directly to measured atomic spectra without requiring reduced-mass corrections for finite nuclear mass.

Numerical values

SI and base units

The hartree, denoted EhE_\mathrm{h}, has a CODATA-recommended value of 4.359 744 722 2060(48)×10−184.359\,744\,722\,2060(48) \times 10^{-18} J in SI units. This energy unit is derived from the base physical constants including the electron mass mem_\mathrm{e}, elementary charge ee, reduced Planck's constant ℏ=h/(2π)\hbar = h/(2\pi), speed of light cc, and vacuum permittivity ϵ0\epsilon_0, via the relation Eh=mec2α2E_\mathrm{h} = m_\mathrm{e} c^2 \alpha^2, where α=e2/(4πϵ0ℏc)\alpha = e^2/(4\pi \epsilon_0 \hbar c) is the fine-structure constant. Equivalently, Eh=mee4(4πϵ0)2ℏ2E_\mathrm{h} = \frac{m_\mathrm{e} e^4}{(4\pi \epsilon_0)^2 \hbar^2}. In the context of energy-time relations, the inverse hartree corresponds to the atomic unit of time τh=ℏ/Eh≈2.418 884 326 5864(26)×10−17\tau_\mathrm{h} = \hbar / E_\mathrm{h} \approx 2.418\,884\,326\,5864(26) \times 10^{-17} s. To illustrate its scale, the hartree represents energies on the order of 10−1810^{-18} J, which is characteristic of electronic binding and transition energies in atomic systems.

Common conversions

In practical applications within physics and chemistry, the hartree (E_h) is frequently converted to electronvolts for electronic structure discussions, where 1 E_h = 27.211386245981(30) eV. Spectroscopic measurements often express energies in wavenumbers, with 1 E_h = 219474.63136314(24) cm^{-1}. In , molar energies are relevant, such that 1 E_h per molecule corresponds to 2625.4996394791(29) kJ/mol or 627.5094743374(69) kcal/mol. The hartree also relates directly to the Rydberg energy (Ry) as 1 E_h = 2 Ry, reflecting its definition as twice the of the . The following table summarizes these conversions based on CODATA 2022 recommendations, including uncertainties for precision in computations:
UnitConversion FactorRelative Standard Uncertainty
eV27.211386245981(30)1.1 × 10^{-12}
cm^{-1}219474.63136314(24)1.1 × 10^{-12}
kJ/mol2625.4996394791(29)1.1 × 10^{-12}
kcal/mol627.5094743374(69)1.1 × 10^{-12}
Rydberg (Ry)2Exact

Physical significance

Connection to hydrogen atom

The hartree energy unit is intrinsically linked to the , serving as twice the absolute value of its ground-state energy in the limit of infinite nuclear mass. In this fundamental system, the ground-state energy E1E_1 is given by E1=−12EhE_1 = -\frac{1}{2} E_h, where EhE_h denotes one hartree. This relation arises because the hartree is defined through , where the 's binding energy sets the scale for electronic energies. Experimentally, the ground-state energy of the actual , accounting for the finite proton mass via the correction, is E1=−13.598433 eVE_1 = -13.598433 \, \mathrm{eV}, which approximates −0.5Eh-0.5 E_h since Eh≈27.211386 eVE_h \approx 27.211386 \, \mathrm{eV}. The precise definition ties Eh=2∣E1(H)∣E_h = 2 |E_1(\mathrm{H})|, where E1(H)E_1(\mathrm{H}) is the ground-state energy for hydrogen with infinite nuclear mass, yielding ∣E1(H)∣=13.605693122994(26) eV|E_1(\mathrm{H})| = 13.605693122994(26) \, \mathrm{eV}. This infinite-mass limit eliminates recoil effects, providing an idealized reference for the unit's physical basis. In practice, the reduced mass μ=me(1−me/Mp)\mu = m_e (1 - m_e/M_p) slightly lowers the energy magnitude for real hydrogen, but the hartree remains anchored to the infinite-mass value for consistency in theoretical calculations. Within the Bohr model of the hydrogen atom, the hartree emerges naturally from the balance of kinetic and potential energies in the electron's circular ground-state orbit. The model posits quantized orbits where the centripetal force equals the Coulomb attraction, leading to a Bohr radius a0a_0 such that the potential energy at this distance is −Eh-E_h. By the virial theorem for inverse-square forces, the time-averaged kinetic energy ⟨T⟩\langle T \rangle equals −12⟨V⟩-\frac{1}{2} \langle V \rangle, so the total energy E=⟨T⟩+⟨V⟩=12⟨V⟩=−⟨T⟩E = \langle T \rangle + \langle V \rangle = \frac{1}{2} \langle V \rangle = -\langle T \rangle. For the ground state, this yields E1=−12EhE_1 = -\frac{1}{2} E_h, with the hartree scaling the magnitudes directly. This connection extends to higher energy levels, where the hydrogen atom's energies form the simple infinite series En=−Eh2n2E_n = -\frac{E_h}{2 n^2} for principal quantum number n=1,2,[3,… ](/page/3Dots)n = 1, 2, [3, \dots](/page/3_Dots). In atomic units, this simplifies to En=−12n2E_n = -\frac{1}{2 n^2}, making transitions between levels yield wavenumbers that are straightforward fractions, which greatly facilitates the analysis of . The unit's design thus provides intuitive numerical simplicity for these exact solutions, underscoring its utility in .

Implications in quantum mechanics

In atomic units, the time-independent for multi-electron atoms takes a parameter-free form, where the , charge, and reduced Planck's constant are set to unity, and energies are expressed in hartrees (EhE_h). This simplification yields −12∑i=1N∇i2ψ−Z∑i=1N1riψ+∑i<j1rijψ=Eψ,-\frac{1}{2} \sum_{i=1}^N \nabla_i^2 \psi - Z \sum_{i=1}^N \frac{1}{r_i} \psi + \sum_{i<j} \frac{1}{r_{ij}} \psi = E \psi, with EE as the dimensionless energy eigenvalue in units of EhE_h, ZZ the nuclear charge, and the coordinates scaled by the . This dimensionless structure facilitates the numerical solution and analytical approximation of wavefunctions for systems beyond the , enabling direct comparison of energy scales across atomic and molecular species. The hartree provides a natural scale for electron correlation effects, which arise from the instantaneous interactions neglected in mean-field approximations like Hartree-Fock. In molecules, these correlation energies—the difference between the exact non-relativistic ground-state energy and the Hartree-Fock limit—typically range from 0.04 to 0.4 EhE_h, depending on the number of s and bonding characteristics; for example, in small closed-shell atoms like , the value is approximately 0.38 EhE_h. This scale underscores the small but crucial role of correlation in achieving chemical accuracy, often requiring post-Hartree-Fock methods for quantitative predictions. The hartree energy is intrinsically tied to the α≈1/137\alpha \approx 1/137, expressed as Eh=α2mec2E_h = \alpha^2 m_e c^2, where mem_e is the rest and cc the . This relation highlights the non-relativistic of while linking to relativistic corrections, which scale as α2\alpha^2 relative to the leading-order energies; for instance, splittings in hydrogen-like atoms are of order (Zα)2Eh/n3(Z \alpha)^2 E_h / n^3, with higher-order terms like the further modulated by α\alpha. Such scaling aids in assessing the validity of non-relativistic approximations for heavier elements. In applied to multi-electron systems, the hartree unit normalizes the unperturbed Hamiltonian (typically the hydrogenic or Hartree-Fock operator) to order 1, allowing perturbation terms like electron-electron repulsions to be treated as expansions in fractions of EhE_h. This facilitates convergence analysis, where second-order corrections for correlation in , for example, contribute about 0.03 EhE_h, with higher orders ensuring rapid convergence for light atoms when expressed relative to EhE_h. The unit thus provides a benchmark for evaluating the perturbative series' reliability across quantum mechanical models.

History

Origins of atomic units

The concept of atomic units emerged from Bohr's 1913 model of the , where the energy scale was defined by the magnitude of the ground-state , expressed as 2π2mee4h22\pi^2 \frac{m_e e^4}{h^2}. This quantity, approximately 13.6 eV, served as a natural reference for the discrete energy levels in the model, En=−2π2mee4h2n2E_n = -\frac{2\pi^2 m_e e^4}{h^2 n^2}, reflecting the quantized orbits of the around the nucleus. Bohr's approach laid the groundwork for scaling atomic phenomena in terms of fundamental constants like the mem_e, charge ee, and Planck's constant hh, though it predated a fully systematic unit system. With the development of in the mid-1920s, early wavefunction calculations for multi-electron atoms employed similar dimensionless forms by normalizing lengths to the and energies to the Rydberg scale. These practices facilitated numerical computations by reducing the equations to forms where key constants were set to unity, emphasizing the hydrogen-like structure as a baseline for more complex systems. In , proposed the atomic unit system in his work on self-consistent field methods for solving the for multi-electron atoms, setting the , charge, and reduced Planck's constant to unity. The framework evolved further with Paul Dirac's formulation of a relativistic for the electron, incorporating into and yielding relativistic corrections to atomic energy levels. Dirac's theory accounted for high velocities near the nucleus, with the cc becoming a key parameter in relativistic extensions of ; however, the non-relativistic hartree energy remained the standard for most atomic calculations due to its sufficiency for lighter elements. Hartree's contributions in applying self-consistent field methods further refined these units for practical use in atomic structure computations. Prior to 1959, the unit—equivalent to twice the Rydberg , or about 27.2 eV—was commonly referred to simply as the "atomic unit of " in theoretical and computational work, without a eponymous name. This terminology underscored its role as a universal scale derived from atomic constants, facilitating comparisons across quantum mechanical models.

Naming and adoption

The hartree unit of was formally named in 1959 by H. Shull and G. G. Hall in their paper "," published in , to honor Douglas Hartree's foundational work on self-consistent field methods for multi-electron atomic systems. Douglas Hartree (1897–1958) was a British and renowned for developing numerical techniques to solve quantum mechanical problems during the 1920s and 1940s, including the Hartree method, which approximates electron densities through iterative self-consistent fields to compute atomic wavefunctions. At the , Hartree pioneered the adaptation of the differential analyzer—an early analog computing device—for performing atomic structure calculations, enabling more accurate numerical solutions to differential equations in quantum theory. The unit saw widespread adoption in the 1960s as computational expanded with the advent of electronic computers, facilitating efficient simulations of molecular systems in a natural, parameter-free framework. In 1993, the International Union of Pure and Applied Chemistry (IUPAC) recommended the symbol EhE_h for the hartree in its Quantities, Units and Symbols in (Green Book), standardizing its notation in physical and chemical literature.

Applications

Computational chemistry

In computational chemistry, the hartree (E_h) serves as the fundamental unit of energy for quantum mechanical calculations, enabling precise handling of electronic structure problems due to its alignment with atomic-scale phenomena. This unit facilitates the computation of molecular energies, where total electronic energies are typically on the order of tens to hundreds of E_h, reflecting the binding of electrons to nuclei. The use of E_h ensures numerical stability and consistency in algorithms, as it avoids scaling factors that could introduce errors in iterative solvers. In Hartree-Fock (HF) theory, the total energy is expressed as the sum of one-electron integrals (kinetic and nuclear attraction terms) and two-electron and exchange integrals, with all contributions evaluated in E_h. For instance, the HF energy for the water molecule converges to approximately -76 E_h using minimal basis sets. Basis set convergence in HF calculations is typically targeted to within 10^{-5} E_h to achieve chemical accuracy, balancing computational cost with precision in molecular properties. This approach underpins self-consistent field methods, where the energy is minimized variationally over molecular orbitals expanded in Gaussian basis functions. Density functional theory (DFT), an extension of HF that incorporates electron correlation via the exchange-correlation functional, also scales all energy components in E_h. The exchange-correlation energy, a key term in the Kohn-Sham equations, is approximated using functionals like LDA or GGA, contributing fractions of E_h that capture binding effects beyond mean-field approximations. Typical binding energies for small molecules, such as atomization energies, range from ~0.1 to 2 E_h, as seen in DFT benchmarks for hydrocarbons and hydrides, highlighting the unit's suitability for quantifying molecular stability. Ab initio methods, including post-HF approaches like MP2 or CCSD(T), perform geometry optimizations and vibrational frequency calculations with internal energies computed in E_h for high precision, though results are often reported in converted units like kcal/mol for interpretability. Software packages such as Gaussian and default to E_h for energy outputs, ensuring seamless integration in workflows for molecular simulations. For example, Gaussian reports SCF energies directly in , while provides total energies like -75.56 E_h for the H2O+ ion in single-point calculations.

Atomic and solid-state physics

In , Hartree atomic units provide a natural framework for solving the for multi-electron atoms by setting fundamental constants such as the me=1m_e = 1, the e=1e = 1, and the reduced Planck's constant ℏ=1\hbar = 1, with the unit of energy defined as the Hartree, approximately 27.211 eV. This system simplifies the non-relativistic Hamiltonian for an NN-electron atom to H=∑i=1N(pi22−Zri)+∑i<j1rijH = \sum_{i=1}^N \left( \frac{p_i^2}{2} - \frac{Z}{r_i} \right) + \sum_{i<j} \frac{1}{r_{ij}}, where ZZ is the nuclear charge, pip_i the , and rijr_{ij} the inter-electron distance, eliminating explicit constants and focusing on electron-nucleus and electron-electron interactions. The Hartree-Fock method, foundational to atomic structure calculations, employs these units to approximate the many-body wavefunction as a of single-particle orbitals, minimizing the energy functional E[Φ]=∑λ=1NIλ+12∑λ,μ(Jλμ−Kλμ)E[\Phi] = \sum_{\lambda=1}^N I_\lambda + \frac{1}{2} \sum_{\lambda,\mu} (J_{\lambda\mu} - K_{\lambda\mu}), where IλI_\lambda is the one-electron , JλμJ_{\lambda\mu} the Coulomb , and KλμK_{\lambda\mu} the exchange . This approach yields ground-state energies and orbital shapes for atoms like and with errors typically under 1% for total energies, enabling predictions of potentials and excitation spectra that align closely with experimental values. For instance, Hartree-Fock calculations in reproduce the ground-state energy as -2.8617 Hartrees, compared to the exact -2.9037 Hartrees, highlighting the method's utility despite neglecting electron correlation. In , Hartree units extend to periodic systems through Hartree-Fock and (DFT) methods, facilitating band structure computations in by normalizing lattice parameters and energies relative to atomic scales. The Hartree potential, representing the classical electrostatic interaction of electrons with the nuclear and electronic , is central to the Kohn-Sham equations in DFT, expressed in as vH(r)=∫n(r′)∣r−r′∣dr′v_H(\mathbf{r}) = \int \frac{n(\mathbf{r}')}{|\mathbf{r} - \mathbf{r}'|} d\mathbf{r}', where n(r)n(\mathbf{r}) is the ; this term accounts for mean-field electron-electron repulsion in solids without explicit many-body effects. Applications include linear combination of atomic orbitals (LCAO) Hartree-Fock calculations for insulators, such as brucite (Mg(OH)2_2), where basis sets like 8-6G for Mg yield band gaps of about 8.5 eV and bulk moduli of 68 GPa, closely matching experiments and revealing ionic Mg-O bonding alongside covalent O-H bonds under pressures up to 45 GPa. Similarly, for NaCl, near-Hartree-Fock-limit basis sets produce valence band widths within 2 mH (milliHartrees) of Bloch-orbital results, with total energies around -621.5 Hartrees per formula unit, demonstrating the method's accuracy for localized Wannier orbitals in ionic crystals. These computations in Hartree units enable quantitative predictions of electronic properties, such as pressure-induced phase transitions, by integrating over Brillouin zones while maintaining computational tractability for unit cells up to 20 atoms.

References

  1. https://physics.nist.gov/cgi-bin/cuu/Value?hr
  2. https://physics.nist.gov/cgi-bin/cuu/Value?hrev
  3. https://www.sizes.com/units/hartree.htm
  4. https://physics.nist.gov/cuu/pdf/nonsi_2010.pdf
  5. https://www.bu.edu/quantum/notes/QuantumMechanics/OneElectronAtom.pdf
  6. https://physics.nist.gov/cuu/pdf/wall_2022.pdf
  7. https://physics.nist.gov/cgi-bin/cuu/Value?hrj
  8. https://link.aps.org/doi/10.1103/RevModPhys.97.025002
  9. https://physics.nist.gov/cgi-bin/cuu/Value?aut
  10. https://physics.nist.gov/cgi-bin/cuu/Value?hrminv
  11. https://physics.nist.gov/cuu/Constants/energy.html
  12. https://physics.nist.gov/PhysRefData/Handbook/Tables/hydrogentable1.htm
  13. https://physics.nist.gov/cgi-bin/cuu/Value?rydhevm1
  14. https://phys.libretexts.org/Bookshelves/University_Physics/University_Physics_(OpenStax)/University_Physics_III_-_Optics_and_Modern_Physics_(OpenStax)/06%3A_Photons_and_Matter_Waves/6.05%3A_Bohrs_Model_of_the_Hydrogen_Atom
  15. https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Quantum_Chemistry_(Blinder)/01%3A_Chapters/1.07%3A_Hydrogen_Atom
  16. https://doi.org/10.1038/s41567-020-01095-x
  17. https://chemphys.uconn.edu/~ch351vc/pdfs/au.pdf
  18. https://pubs.acs.org/doi/10.1021/jp302170r
  19. https://ocw.mit.edu/courses/8-06-quantum-physics-iii-spring-2018/439fc15f7ed10dd76c69dc3f7fea600e_MIT8_06S18ch2.pdf
  20. http://www.damtp.cam.ac.uk/user/tong/aqm/topics3.pdf
  21. https://link.aps.org/doi/10.1103/PhysRev.146.1
  22. https://farside.ph.utexas.edu/teaching/qm/Quantum/node44.html
  23. https://home.cern/news/news/physics/atomic-flashback-century-bohr-model
  24. https://www.cambridge.org/core/journals/proceedings-of-the-cambridge-philosophical-society/article/abs/wave-mechanics-of-an-atom-with-a-non-coulomb-central-field-part-ia-methods/0A3D4A6A7D1A9E4B0B0A7E4B0B0A7E4B
  25. https://royalsocietypublishing.org/doi/10.1098/rspa.1928.0023
  26. https://www.aps.org/apsnews/2024/11/mathematical-intuition-dirac-quantum-mechanics
  27. https://www.nature.com/articles/1841559a0
  28. https://mathshistory.st-andrews.ac.uk/Biographies/Hartree/
  29. https://collection.sciencemuseumgroup.org.uk/objects/co59975/manchester-university-differential-analyser
  30. https://iupac.org/wp-content/uploads/2019/05/IUPAC-GB3-2012-2ndPrinting-PDFsearchable.pdf
  31. https://bohr.physics.berkeley.edu/classes/221/1112/notes/hartfock.pdf
  32. https://dft.uci.edu/pubs/EPB96.pdf
  33. https://rruff.geo.arizona.edu/doclib/am/vol76/AM76_1769.pdf
  34. https://arxiv.org/pdf/cond-mat/9803379
Add your contribution
Related Hubs
User Avatar
No comments yet.