HETEROCYCLIC PYRIDINIUM BETAINES, A NEW CLASS OF 2ND-ORDER NONLINEAR-OPTICAL MATERIALS - COMBINED THEORETICAL AND EXPERIMENTAL INVESTIGATION OF FIRST-ORDER HYPERPOLARIZABILITY THROUGH AB-INITIO, INDO S, AND HYPER-RAYLEIGH SCATTERING/
J. Abe et al., HETEROCYCLIC PYRIDINIUM BETAINES, A NEW CLASS OF 2ND-ORDER NONLINEAR-OPTICAL MATERIALS - COMBINED THEORETICAL AND EXPERIMENTAL INVESTIGATION OF FIRST-ORDER HYPERPOLARIZABILITY THROUGH AB-INITIO, INDO S, AND HYPER-RAYLEIGH SCATTERING/, JOURNAL OF PHYSICAL CHEMISTRY B, 101(4), 1997, pp. 576-582
The first hyperpolarizability, beta, of one of the simplest heterocycl
ic pyridinium betaines, (1-pyridinio)-benzimidazolate, was measured ex
perimentally with the hyper-Rayleigh scattering technique and compared
to the calculated values obtained by the semiempirical INDO/S and ab
initio molecular orbital methods. Heterocyclic pyridinium betaines are
characterized by their zwitterionic character where a negatively char
ged aromatic electron-donating group and a positively charged aromatic
electron-withdrawing group are linked directly. The experimentally ob
tained \beta\ value, (115 +/- 25) x 10(-30) cm(5) esu(-1), was in good
agreement with those derived from the LNDO/S calculations. The first
excited state was found to be characterized by a strong intramolecular
charge-transfer state, when the electron transition occurs from a neg
atively charged aromatic electron-donating group (benzimidazole ring)
to a directly linked, positively charged aromatic electron-withdrawing
group (pyridinium ring). This nature of the excited state would give
rise to a large difference between the dipole moments in the excited a
nd ground states and would contribute to enlargement of beta values.