Relativistic total energy using regular approximations
10.1063/1.467943
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

In this paper we will discuss relativistic total energies using the zeroth order regular approximation (ZORA). A simple scaling of the ZORA one-electron Hamiltonian is shown to yield energies for the hydrogenlike atom that are exactly equal to the Dirac energies. The regular approximation is not gauge invariant in each order, but the scaled ZORA energy can be shown to be exactly gauge invariant for hydrogenic ions. It is practically gauge invariant for many-electron systems and proves superior to the (unscaled) first order regular approximation for atomic ionization energies. The regular approximation, if scaled, can therefore be applied already in zeroth order to molecular bond energies. Scalar relativistic density functional all-electron and frozen core calculations on diatomics, consisting of copper, silver, and gold and their hydrides are presented. We used exchange-correlation energy functionals commonly used in nonrelativistic calculations; both in the local-density approximation (LDA) and including density-gradient (‘‘nonlocal’’) corrections (NLDA). At the NLDA level the calculated dissociation energies are all within 0.2 eV from experiment, with an average of 0.1 eV. All-electron calculations for Au2 and AuH gave results within 0.05 eV of the frozen core calculations.

Bibliography

van Lenthe, E., Baerends, E. J., & Snijders, J. G. (1994). Relativistic total energy using regular approximations. The Journal of Chemical Physics, 101(11), 9783–9792.

Authors 3
  1. E. van Lenthe (first)
  2. E. J. Baerends (additional)
  3. J. G. Snijders (additional)
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Dates
Type When
Created 23 years, 1 month ago (July 26, 2002, 8:32 a.m.)
Deposited 1 year, 6 months ago (Feb. 10, 2024, 7:13 p.m.)
Indexed 14 hours, 17 minutes ago (Sept. 6, 2025, 4:19 p.m.)
Issued 30 years, 9 months ago (Dec. 1, 1994)
Published 30 years, 9 months ago (Dec. 1, 1994)
Published Print 30 years, 9 months ago (Dec. 1, 1994)
Funders 0

None

@article{van_Lenthe_1994, title={Relativistic total energy using regular approximations}, volume={101}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.467943}, DOI={10.1063/1.467943}, number={11}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={van Lenthe, E. and Baerends, E. J. and Snijders, J. G.}, year={1994}, month=dec, pages={9783–9792} }