Analytical evaluation of first-order electrical properties based on the spin-free Dirac-Coulomb Hamiltonian

摘要

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, CH_nF _(3 - n)I, 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.