Spin-free Dirac-Coulomb calculations augmented with a perturbative treatment of spin-orbit effects at the Hartree-Fock level
- Institute for Theoretical Chemistry, Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712 (United States)
- Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, N-0315 Oslo (Norway)
- Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz (Germany)
A perturbative approach to compute second-order spin-orbit (SO) corrections to a spin-free Dirac-Coulomb Hartree-Fock (SFDC-HF) calculation is suggested. The proposed scheme treats the difference between the DC and SFDC Hamiltonian as perturbation and exploits analytic second-derivative techniques. In addition, a cost-effective scheme for incorporating relativistic effects in high-accuracy calculations is suggested consisting of a SFDC coupled-cluster treatment augmented by perturbative SO corrections obtained at the HF level. Benchmark calculations for the hydrogen halides HX, X = F-At as well as the coinage-metal fluorides CuF, AgF, and AuF demonstrate the accuracy of the proposed perturbative treatment of SO effects on energies and electrical properties in comparison with the more rigorous full DC treatment. Furthermore, we present, as an application of our scheme, results for the electrical properties of AuF and XeAuF.
- OSTI ID:
- 22251286
- Journal Information:
- Journal of Chemical Physics, Vol. 139, Issue 21; Other Information: (c) 2013 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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