Universal formulation of second-order generalized Møller–Plesset perturbation theory for a spin-dependent two-component relativistic many-electron Hamiltonian

Masahiko Nakano, Junji Seino, Hiromi Nakai

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2 Citations (Scopus)

Abstract

We have derived and implemented a universal formulation of the second-order generalized Møller–Plesset perturbation theory (GMP2) for spin-dependent (SD) two-component relativistic many-electron Hamiltonians, such as the infinite-order Douglas–Kroll–Hess Hamiltonian for many-electron systems, which is denoted as IODKH/IODKH. Numerical assessments for He- and Ne-like atoms and 16 diatomic molecules show that the MP2 correlation energies with IODKH/IODKH agree well with those calculated with the four-component Dirac–Coulomb (DC) Hamiltonian, indicating a systematic improvement on the inclusion of relativistic two-electron terms. The present MP2 scheme for IODKH/IODKH is demonstrated to be computationally more efficient than that for DC.

Original languageEnglish
Pages (from-to)137-144
Number of pages8
JournalChemical Physics Letters
Volume675
DOIs
Publication statusPublished - 2017 May 1

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Hamiltonians
perturbation theory
formulations
Electrons
electrons
diatomic molecules
inclusions
Atoms
Molecules
atoms
energy

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Universal formulation of second-order generalized M{\o}ller–Plesset perturbation theory for a spin-dependent two-component relativistic many-electron Hamiltonian",
abstract = "We have derived and implemented a universal formulation of the second-order generalized M{\o}ller–Plesset perturbation theory (GMP2) for spin-dependent (SD) two-component relativistic many-electron Hamiltonians, such as the infinite-order Douglas–Kroll–Hess Hamiltonian for many-electron systems, which is denoted as IODKH/IODKH. Numerical assessments for He- and Ne-like atoms and 16 diatomic molecules show that the MP2 correlation energies with IODKH/IODKH agree well with those calculated with the four-component Dirac–Coulomb (DC) Hamiltonian, indicating a systematic improvement on the inclusion of relativistic two-electron terms. The present MP2 scheme for IODKH/IODKH is demonstrated to be computationally more efficient than that for DC.",
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T1 - Universal formulation of second-order generalized Møller–Plesset perturbation theory for a spin-dependent two-component relativistic many-electron Hamiltonian

AU - Nakano, Masahiko

AU - Seino, Junji

AU - Nakai, Hiromi

PY - 2017/5/1

Y1 - 2017/5/1

N2 - We have derived and implemented a universal formulation of the second-order generalized Møller–Plesset perturbation theory (GMP2) for spin-dependent (SD) two-component relativistic many-electron Hamiltonians, such as the infinite-order Douglas–Kroll–Hess Hamiltonian for many-electron systems, which is denoted as IODKH/IODKH. Numerical assessments for He- and Ne-like atoms and 16 diatomic molecules show that the MP2 correlation energies with IODKH/IODKH agree well with those calculated with the four-component Dirac–Coulomb (DC) Hamiltonian, indicating a systematic improvement on the inclusion of relativistic two-electron terms. The present MP2 scheme for IODKH/IODKH is demonstrated to be computationally more efficient than that for DC.

AB - We have derived and implemented a universal formulation of the second-order generalized Møller–Plesset perturbation theory (GMP2) for spin-dependent (SD) two-component relativistic many-electron Hamiltonians, such as the infinite-order Douglas–Kroll–Hess Hamiltonian for many-electron systems, which is denoted as IODKH/IODKH. Numerical assessments for He- and Ne-like atoms and 16 diatomic molecules show that the MP2 correlation energies with IODKH/IODKH agree well with those calculated with the four-component Dirac–Coulomb (DC) Hamiltonian, indicating a systematic improvement on the inclusion of relativistic two-electron terms. The present MP2 scheme for IODKH/IODKH is demonstrated to be computationally more efficient than that for DC.

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