Perturbative treatment of spin-orbit coupling within spin-free exact two-component theory
- Institute for Theoretical Chemistry, Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712 (United States)
- Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz (Germany)
This work deals with the perturbative treatment of spin-orbit-coupling (SOC) effects within the spin-free exact two-component theory in its one-electron variant (SFX2C-1e). We investigate two schemes for constructing the SFX2C-1e SOC matrix: the SFX2C-1e+SOC [der] scheme defines the SOC matrix elements based on SFX2C-1e analytic-derivative theory, hereby treating the SOC integrals as the perturbation; the SFX2C-1e+SOC [fd] scheme takes the difference between the X2C-1e and SFX2C-1e Hamiltonian matrices as the SOC perturbation. Furthermore, a mean-field approach in the SFX2C-1e framework is formulated and implemented to efficiently include two-electron SOC effects. Systematic approximations to the two-electron SOC integrals are also proposed and carefully assessed. Based on benchmark calculations of the second-order SOC corrections to the energies and electrical properties for a set of diatomic molecules, we show that the SFX2C-1e+SOC [der] scheme performs very well in the computation of perturbative SOC corrections and that the “2eSL” scheme, which neglects the (SS|SS)-type two-electron SOC integrals, is both efficient and accurate. In contrast, the SFX2C-1e+SOC [fd] scheme turns out to be incompatible with a perturbative treatment of SOC effects. Finally, as a first chemical application, we report high-accuracy calculations of the {sup 201}Hg quadrupole-coupling parameters of the recently characterized ethylmercury hydride (HHgCH{sub 2}CH{sub 3}) molecule based on SFX2C-1e coupled-cluster calculations augmented with second-order SOC corrections obtained at the Hartree-Fock level using the SFX2C-1e+SOC [der]/2eSL scheme.
- OSTI ID:
- 22310727
- Journal Information:
- Journal of Chemical Physics, Vol. 141, Issue 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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