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J Chem Phys. 2016 Nov 14;145(18):184104.

Calculations of electric dipole moments and static dipole polarizabilities based on the two-component normalized elimination of the small component method.

Author information

1
Department of Chemistry, Southern Methodist University, 3215 Daniel Ave., Dallas, Texas 75275-0314, USA.

Abstract

The analytical energy gradient and Hessian of the two-component Normalized Elimination of the Small Component (2c-NESC) method with regard to the components of the electric field are derived and used to calculate spin-orbit coupling (SOC) corrected dipole moments and dipole polarizabilities of molecules, which contain elements with high atomic number. Calculated 2c-NESC dipole moments and isotropic polarizabilities agree well with the corresponding four-component-Dirac Hartree-Fock or density functional theory values. SOC corrections for the electrical properties are in general small, but become relevant for the accurate prediction of these properties when the molecules in question contain sixth and/or seventh period elements (e.g., the SO effect for At2 is about 10% of the 2c-NESC polarizability). The 2c-NESC changes in the electric molecular properties are rationalized in terms of spin-orbit splitting and SOC-induced mixing of frontier orbitals with the same j = l + s quantum numbers.

PMID:
27846684
DOI:
10.1063/1.4964765

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