Static and dynamic coupled perturbed Hartree-Fock vibrational (hyper)polarizabilities of polyacetylene calculated by the finite field nuclear relaxation method

V. Lacivita , Michel Rérat (1) , B. Kirtman , R. Orlando , M. Ferrabone , Roberto Dovesi

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux

The vibrational contribution to static and dynamic (hyper)polarizability tensors of polyacetylene are theoretically investigated. Calculations were carried out by the finite field nuclear relaxation (FF-NR) method for periodic systems, newly implemented in the CRYSTAL code, using the coupled perturbed Hartree-Fock scheme for the required electronic properties. The effect of the basis set is also explored, being particularly important for the non-periodic direction perpendicular to the polymer plane. Components requiring a finite (static) field in the longitudinal direction for evaluation by the FF-NR method were not evaluated. The extension to that case is currently being pursued. Whereas the effect on polarizabilities is relatively small, in most cases the vibrational hyperpolarizability tensor component is comparable to, or larger than the corresponding static electronic contribution. © 2012 American Institute of Physics.

Domaines: Chimie théorique et/ou physique

V. Lacivita, Michel Rérat, B. Kirtman, R. Orlando, M. Ferrabone, et al.. Static and dynamic coupled perturbed Hartree-Fock vibrational (hyper)polarizabilities of polyacetylene calculated by the finite field nuclear relaxation method. Journal of Chemical Physics, 2012, 137 (1), ⟨10.1063/1.4731266⟩. ⟨hal-01610576⟩