The correlation, relativistic, and vibrational contributions to the dipole moments, polarizabilities, and first and second hyperpolarizabilities of ZnS, CdS, and HgS
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Media type:
E-Article
Title:
The correlation, relativistic, and vibrational contributions to the dipole moments, polarizabilities, and first and second hyperpolarizabilities of ZnS, CdS, and HgS
Contributor:
Raptis, S. G.;
Papadopoulos, M. G.;
Sadlej, A. J.
Description:
<jats:p>The dipole moments, dipole polarizabilities, and the first and second hyperpolarizabilities of the Group IIb sulfides have been calculated by using different high-level-correlated methods and including both the relativistic and vibrational contributions. The electron correlation effects have been studied at the levels of the second-order Møller–Plesset perturbation theory and the coupled-cluster methods. The relativistic contributions and the interference relativistic-correlation effects have been accounted for by using the spin-averaged Douglas–Kroll approximation. The vibrational properties (pure vibrational contributions and the zero-point vibrational averaging corrections) have been computed using CCSD(T) theory with and without relativistic corrections. The present pure electronic nonrelativistic results exhibit essentially the same pattern as that observed for similar molecules studied earlier. Most of the relativistic effects on dipole moments and dipole polarizabilities is accounted for at the level of the SCF approximation and rapidly increases with the nuclear charge of the heavy atom. The contribution of the relativistic-correlation interference terms has been found to be quite significant for axial components of the first and second dipole hyperpolarizabilities. All the properties reported here are static. This is the first study which reports on the relativistic contributions to hyperpolarizabilities as well as on vibrational effects upon both polarizabilities and hyperpolarizabilities of heavy metal (Group IIb) involving compounds. Thus the reported results add to the knowledge and understanding of the importance of the electron correlation, relativistic, and vibrational effects on electric properties of heavy molecules and extend the corresponding data beyond the linear response approximation. The reliability of the computed data is discussed in terms of the underlying approximations and limitations of methods used in this study.</jats:p>