Examination of accuracy of electron-electron Coulomb interactions in two-component relativistic methods

Junji Seino; Masahiko Hada

doi:10.1016/j.cplett.2008.07.009

Examination of accuracy of electron-electron Coulomb interactions in two-component relativistic methods

Junji Seino, Masahiko Hada^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

48 Citations (Scopus)

Abstract

We examined the accuracy of two-component quantum-chemical methods, focusing on relativistic treatments of the electron-electron Coulomb interaction. We observed SCF energies, orbital energies, and spin-orbit splittings of He-like and noble-gas atoms up to Uuo (atomic number 118). These were calculated by using either the two-electron term generated by the first-order Foldy-Wouthuysen (2e-FW1) or the infinite-order Douglas-Kroll-Hess (2e-IODKH) transformation, both of which are incorporated with the one-electron terms generated by the IODKH transformation. The 2e-FW1 term was much superior to the lowest-order (c^-2) two-electron Breit-Pauli correction, and the 2e-IODKH term gave energies essentially equivalent to four-component Dirac-Fock/Coulomb energies.

Original language	English
Pages (from-to)	327-331
Number of pages	5
Journal	Chemical Physics Letters
Volume	461
Issue number	4-6
DOIs	https://doi.org/10.1016/j.cplett.2008.07.009
Publication status	Published - 2008 Aug 20
Externally published	Yes

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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title = "Examination of accuracy of electron-electron Coulomb interactions in two-component relativistic methods",

abstract = "We examined the accuracy of two-component quantum-chemical methods, focusing on relativistic treatments of the electron-electron Coulomb interaction. We observed SCF energies, orbital energies, and spin-orbit splittings of He-like and noble-gas atoms up to Uuo (atomic number 118). These were calculated by using either the two-electron term generated by the first-order Foldy-Wouthuysen (2e-FW1) or the infinite-order Douglas-Kroll-Hess (2e-IODKH) transformation, both of which are incorporated with the one-electron terms generated by the IODKH transformation. The 2e-FW1 term was much superior to the lowest-order (c-2) two-electron Breit-Pauli correction, and the 2e-IODKH term gave energies essentially equivalent to four-component Dirac-Fock/Coulomb energies.",

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AU - Hada, Masahiko

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AB - We examined the accuracy of two-component quantum-chemical methods, focusing on relativistic treatments of the electron-electron Coulomb interaction. We observed SCF energies, orbital energies, and spin-orbit splittings of He-like and noble-gas atoms up to Uuo (atomic number 118). These were calculated by using either the two-electron term generated by the first-order Foldy-Wouthuysen (2e-FW1) or the infinite-order Douglas-Kroll-Hess (2e-IODKH) transformation, both of which are incorporated with the one-electron terms generated by the IODKH transformation. The 2e-FW1 term was much superior to the lowest-order (c-2) two-electron Breit-Pauli correction, and the 2e-IODKH term gave energies essentially equivalent to four-component Dirac-Fock/Coulomb energies.

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Examination of accuracy of electron-electron Coulomb interactions in two-component relativistic methods

Abstract

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