Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 134, Issue 24, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.3601056
Keywords
coupled cluster calculations; hydrogen compounds; organic compounds; perturbation theory; relativistic corrections; spin-orbit interactions
Funding
- Deutsche Forschungsgemeinschaft (DFG) [GA370/5-1]
- Fonds der Chemischen Industrie
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We report an analytical scheme for the calculation of first-order electrical properties using the spin-free Dirac-Coulomb (SFDC) Hamiltonian, thereby exploiting the well-developed density-matrix formulations in nonrelativistic coupled-cluster (CC) derivative theory. Orbital relaxation effects are fully accounted for by including the relaxation of the correlated orbitals with respect to orbitals of all types, viz., frozen-core, occupied, virtual, and negative energy state orbitals. To demonstrate the applicability of the presented scheme, we report benchmark calculations for first-order electrical properties of the hydrogen halides, HX with X = F, Cl, Br, I, At, and a first application to the iodo(fluoro)methanes, CHnF3-nI, n = 0-3. The results obtained from the SFDC calculations are compared to those from nonrelativistic calculations, those obtained via leading-order direct perturbation theory as well as those from full Dirac-Coulomb calculations. It is shown that the full inclusion of spin-free (SF) relativistic effects is necessary to obtain accurate first-order electrical properties in the presence of fifth-row elements. The SFDC scheme is also recommended for applications to systems containing lighter elements because it introduces no extra cost in the rate-determining steps of a CC calculation in comparison to the nonrelativistic case. On the other hand, spin-orbit contributions are generally small for first-order electrical properties of closed-shell molecules and may be handled efficiently by means of perturbation theory. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3601056]
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