TY - JOUR

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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U2 - 10.1016/j.cplett.2017.03.027

DO - 10.1016/j.cplett.2017.03.027

M3 - Article

AN - SCOPUS:85015401546

VL - 675

SP - 137

EP - 144

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

ER -