Missing-orbital analysis of molecular hyperpolarizability β calculated by a simplified sum-over-states method. Enhancement of the off-diagonal component βzxx
✍ Scribed by Mutsumi Tomonari; Norio Ookubo; Toshikazu Takada
- Publisher
- Elsevier Science
- Year
- 1993
- Tongue
- English
- Weight
- 781 KB
- Volume
- 215
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
The off-diagonal component of the first-order hyperpolarixability tensor 8, of Czv molecules, e.g. substituted polyynes and benxenes, has been calculated by a simplified sum-over-states method. The missing-orbital analysis of the calculated results reveals that excitations from a2 and b2 orbitals contribute cooperatively to /I-suggesting an insufficiency of the two-state model to describefi,. Increasing the number of occupied a2 orbitals enhances the magnitude of/J-For the Czv molecule with a2 orbitals widely extended in the x direction, jl_ can exceed pun as found in g-amino-1 O-cyanoanthracene having a /I-about twice as large as AZ*.