BASIS-SET EFFECTS ON THE NONLINEAR-OPTICAL PROPERTIES OF SELECTED LINEAR DIACETYLENES

Calculations of the nonlinear optical properties (hyperpolarizabilities beta and gamma) of a series of substituted linear diacetylenes have been performed using time-dependent Hartree-Fock (TDHF) theory. Several different basis sets of increasingly improved quality have been used with an incident optical frequency corresponding to the Nd:YAG laser fundamental (1064 nm). In addition, the frequency dependence of both beta and gamma has been studied for all molecules using a modest basis set. Our results yield a previously unreported Linear correlation between the frequency-dependent and static values of the hyperpolarizabilities for a variety of nonlinear optical processes. This dispersion correction appears to be relatively insensitive to basis set.