Ab initio calculations of the second dynamic hyperpolarizability of LiH by means of floquet theory approach

A.V. Shtoff , Michel Rérat (1) , S.I. Gusarov

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

Floquet theory is used to describe the response of a molecule to applied radiation electric field. The method of ab initio calculation of frequency dependent (hyper)polarizabilities based on combination of perturbation theory with the finite field method has been developed. Electron correlation is taken into account by means of the CIPSI algorithm. The total wave function expansion involves spectral, pseudo-spectral states and polynomial terms. The developed approach is applied to the calculation of the second hyperpolarizability of the lithium hydride molecule subjected to the superposition of harmonic and static electric fields. The method can be used to calculate the higher order nonlinear properties of molecules.

Domaines: Chimie théorique et/ou physique

A.V. Shtoff, Michel Rérat, S.I. Gusarov. Ab initio calculations of the second dynamic hyperpolarizability of LiH by means of floquet theory approach. The European Physical Journal D : Atomic, molecular, optical and plasma physics, 2001, 15 (2), pp.199-208. ⟨10.1007/s100530170166⟩. ⟨hal-01610607⟩