SUM OVER ORBITALS SCALING OF THE 2ND HYPERPOLARIZABILITIES OF POLYENIC CHAINS - A CASE-STUDY

A sum over molecular orbitals scheme with a 6-31G basis set is tested to calculate the static second hyperpolarisabilities gamma of polyenic chains with N double bonds (5 less than or equal to N less than or eq ual to 80). On scaling ab initio values by a factor that 'substitutes' the HOMO-LUMO gap with the optical gap, the calculated gamma s are in good agreement with experimental results reported on substituted poly enic chains up to roughly 70 double bonds. This agreement is taken to indicate that the present simplified procedure can behave as an effect ive hamiltonian which may find further application. Alternatively, one can postulate that the nature of the response in polyenic chains can be reduced to a function of the molecular orbitals only. (C) 1998 Else vier Science B.V.