Comments of the vibronic linewidth of an isolated resonance of a higher electronic state

✍ Scribed by Benjamin Sharf; Robert Silbey

• Publisher: Elsevier Science
• Year: 1969
• Tongue: English
• Weight: 241 KB
• Volume: 4
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(69)85003-7

✦ Synopsis

The linewidth of a higher electronic transition interactin, v with a lower continuum of vibronic states is calculated using a simple model. The calculated linewidth is two orders of magnitude smaller than observed.

Experimental

studies have established the fact that, with a few rare exceptions, radiative emission

does not occur from excited states of large molecules higher than the lowest excited state of agiven multiplicity.

Many theories have been put forward to explain the channels of "radiationless transitions" responsible for this phenomenon.

An intimately related phenomenon is the diffuseness of the absorption spectra of thsse higher electronic transitions, traced by many authors to line broadening caused by vibronic interactions. Recently quantitative descriptions based on time-independent theory were proposed independently by Bixon and Jortner [l] and by Henry and Kasha [2], Rhodes [3], and Gardner and Kasha [4]. ExperimentalLy encountered linewidths of individual vibronic transitions to higher excited electronic