MISSING-ORBITAL ANALYSIS OF MOLECULAR HYPERPOLARIZABILITY-BETA CALCULATED BY A SIMPLIFIED SUM-OVER-STATES METHOD - ENHANCEMENT OF THE OFF-DIAGONAL COMPONENT-BETA(ZXX)

Authors
TOMONARI M OOKUBO N TAKADA T
Citation
M. Tomonari et al., MISSING-ORBITAL ANALYSIS OF MOLECULAR HYPERPOLARIZABILITY-BETA CALCULATED BY A SIMPLIFIED SUM-OVER-STATES METHOD - ENHANCEMENT OF THE OFF-DIAGONAL COMPONENT-BETA(ZXX), Chemical physics letters, 215(1-3), 1993, pp. 45-52
Citations number
16
Categorie Soggetti
Physics, Atomic, Molecular & Chemical
Journal title
Chemical physics letters → ACNP
ISSN journal
00092614
Volume
215
Issue
1-3
Year of publication
1993
Pages
45 - 52
Database
ISI
SICI code
0009-2614(1993)215:1-3<45:MAOMHC>2.0.ZU;2-K
Abstract
The off-diagonal component of the first-order hyperpolarizability tens or beta(zxx) Of C2v molecules, e.g. substituted polyynes and benzenes, has been calculated by a simplified sum-over-states method. The missi ng-orbital analysis of the calculated results reveals that excitations from a2 and b2 orbitals contribute cooperatively to beta(zxx), sugges ting an insufficiency of the two-state model to describe beta(zxx). In creasing the number of occupied a2 orbitals enhances the magnitude of beta(zxx). For the C2v molecule with a2 orbitals widely extended in th e x direction, beta(zxx) can exceed beta(zzz) as found in 9-amino-10-c yanoanthracene having a beta(zxx) about twice as large as beta(zzz).