Static and frequency dependent polarizabilities and hyperpolarizabilities of H2Sn

Abstract

The structure–polarization relationship was investigated in a series of polysulfanes, H2Sn. The reported results demonstrate that the forms of change of the polarizability components, αii, and the second hyperpolarizability components, γiiii, as well as the average values α and γ, respectively, of H2Sn with n are similar. This shows that polarizability components can be easily used to determine corresponding hyperpolarizability data. A remarkable change of the hyperpolarizabilities with the molecular geometry of H2Sn was found. This result can be used for the design of nonlinear optical materials with optimum properties. The present study uses the flexible σ bonded H2Sn and is complementary to the works that considered the effect of conformational changes of π-conjugated systems on their hyperpolarizabities. The present computations were performed using the semiempirical approaches MNDO and MNDO/d, as well as ab initio methods with STO-3G, extended with polarization and diffuse functions, and [3s2p/7s5p2d] sets for H2Sn. At the ab initio level, the electronic and the vibrational contributions to polarizabilities and hyperpolarizabilities were both computed for several members of H2Sn. The frequency dependence of the above contributions and the static limit were discussed. Electron correlation was taken into account for several test cases using MP2 theory. The selected methods and the variety of the approximations on which they rely allow the systematic consideration of the effect of changes of the geometry of H2Sn on their polarizabilities and second hyperpolarizabilities. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1698–1715, 1998