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Title: Performance of an atomic mean-field spin–orbit approach within exact two-component theory for perturbative treatment of spin–orbit coupling

Journal Article · · Molecular Physics
 [1];  [1]
  1. Johns Hopkins Univ., Baltimore, MD (United States)
+ Show Author Affiliations

The paper reports development of an atomic mean-field (AMF) spin–orbit approach within the spin-free exact two-component theory in its one-electron variant (SFX2C-1e), a new relativistic quantum-chemical method for treating spin-orbit coupling in molecules. The effective one-electron spin–orbit integral matrix in the four-component representation is assembled as a direct sum of one-centre spin–orbit integral matrices with the mean-field two-electron contributions evaluated using atomic SFX2C-1e Hartree–Fock density matrices. It is then transformed into two-component representation using analytic SFX2C-1e energy derivative formulation. The resulting two-component spin–orbit integral matrix is by design suitable for use in perturbative calculations of spin–orbit coupling, treating SFX2C-1e wavefunctions as unperturbed states. The accuracy of the present AMF approach has been demonstrated using benchmark calculations of spin–orbit splittings for representative diatomic radicals at the equation-of-motion coupled-cluster singles and doubles level. In conclusion, to demonstrate the applicability and accuracy of the present perturbative spin–orbit scheme in calculations of challenging heavy-element containing systems, a thorough computational investigation of six low-lying electronic states of ThO+ is reported.

Research Organization:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0020317
OSTI ID:
1684918
Journal Information:
Molecular Physics, Vol. 118, Issue 19-20; ISSN 0026-8976
Publisher:
Taylor & FrancisCopyright Statement
Country of Publication:
United States
Language:
English

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  • Wahlgren, Ulf; Sjøvoll, Merethe; Fagerli, Hilde
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Related Subjects

97 MATHEMATICS AND COMPUTING
74 ATOMIC AND MOLECULAR PHYSICS
Relativistic effects
relativistic quantum mechanics
spin-orbit coupling
exact two-component theory
actinide spectroscopy
mean field spin orbit approach