Effects of anharmonicities on radiationless transitions in large molecules

✍ Scribed by Y. Mikami; K. Mizunoya; T. Nakajima

• Publisher: Elsevier Science
• Year: 1975
• Tongue: English
• Weight: 722 KB
• Volume: 30
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(75)80010-8

✦ Synopsis

A new computational method to account for the effect of anharmonicities on non-radhtive decay ratesofkge molecules in the statisti~l limit is given by using expansions of the generating functions which have been used successfully 'ffl multiphor;on processes. This method is free from the ambiguity which, as in previous conventional methods, arks from the factorization which separates the decay rate into a product of an electronic term, a Franck-Condon rector and a densitjr of final states. The rate expressidn is asymmetric with respect to the sign of the displacement of the accepting modes.

Actual

calculations ae performed for a model molecule which closely resembles berzene. The numerical data for the decay rate exceed the results of the harmonic approximation by about two.orders of magnitude.