ISSN:
1572-9613
Keywords:
Photochemical isomerization
;
Kramers' equation
;
Kramers' turnover
;
frequency-dependent friction
;
intramolecular vibrational relaxation
;
barrier crossing
;
rovibrational density of states
Source:
Springer Online Journal Archives 1860-2000
Topics:
Physics
Notes:
Abstract Photochemical isomerization in stilbene and diphenyl butadiene has been studied as a model for activated barrier crossing. Experiments have been carried out from isolated molecule conditions up to 3000 atm pressure in solution-phase samples. The qualitative features predicted by Kramers theory are observed. The system undergoes a transition from energy-controlled to diffusion-controlled behavior in the high-pressure gas phase. The influences of multidimensionality, intramolecular vibrational relaxation, and frequency dependent friction are discussed.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01010842
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