화학공학소재연구정보센터
Journal of Chemical Physics, Vol.114, No.2, 735-745, 2001
Vibrational effects on electric properties of cyclopropenone and cyclopropenethione
Vibrational contributions to the dipole polarizabilities and hyperpolarizabilities of cyclopropenone and cyclopropenethione are reported. Simultaneous calculations have been carried out for the respective saturated and noncyclic counterparts of these molecules. The results have been analyzed and interpreted in terms of different structural and electronic features of the studied molecules: i.e., the oxygen-sulfur replacement, the saturation of the carbon ring, and the removal of the intramolecular strain. For static dipole polarizabilities the vibrational contribution computed at the molecular equilibrium geometry can account for more than 10% of the total value for a given component of the tensor. Both the zero-point vibrational average and pure vibrational terms are important for most of the studied molecules. In the case of the first dipole hyperpolarizability the total vibrational correction is dominated by the pure vibrational term. The vibrational corrections to dipole polarizabilities show certain regularities which can be interpreted in terms of the electronic structure of the investigated molecules. Much less clear is the pattern of behavior for the first dipole hyperpolarizability. It has been found, however, that the analysis of these data is greatly facilitated by the separate consideration of the nuclear relaxation and curvature terms. Limited study of the frequency dependence of the calculated vibrational corrections shows that in the case of the dipole polarizability, they are almost quenched to zero. In contrast, at nonzero frequencies, the vibrational contribution to the first dipole hyperpolarizability tensor beta(-omega;omega ,0), which determines the so-called electro-optic Pockels effect, can be as important as the pure electronic term.