Vibrational versus electronic first hyperpolarizabilities of mono- and disubstituted benzenes: An ab initio coupled Hartree-Fock investigation

Abstract

Static electronic and vibrational longitudinal first hyperpolarizabilities (βLe(0) and βLv(0)) of a series of mono- and disubstituted benzenes were calculated at the Hartree–Fock 6-31G level by using coupled Hartree–Fock and the double harmonic oscillator approximations, respectively. Although the βLv(0)/βLe(0) ratio is slightly larger than unity and rather constant with respect to the substituent(s), it turns out, for the monosubstituted compounds, that the variations of βLe(0) upon substitution can be most accounted for by the mesomeric effects, whereas for βLv(0), the inductive effects are also of importance. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 65: 689–696, 1997