Direct observation of non-RRKM behavior in femtosecond photophysically activated reactions

I-Ren Lee, Wei Kan Chen, Yu Chieh Chung, Po Yuan Cheng

研究成果: 雜誌貢獻文章同行評審

20 引文 斯高帕斯(Scopus)


A nonstatistical behavior has been observed in the photodissociation of two acyl cyanide compounds, R-C(O)-CN, where R = methyl and tert-butyl groups. The initial activation was achieved by femtosecond two-photon excitation followed by ultrafast internal conversion.The excited-state dissociation dynamics was followed in real time by monitoring the temporal evolution of CN (X) products. The observed product appearance time constants are in picosecond time scales and are markedly similar for the two compounds studied. Our analyzes revealed that the excited-state dissociation rate does not decrease with molecular size as much as statistical rate theory predicts, suggesting a nonergodic system in which the available vibrational energy does not redistributed statistically among all modes before the bond breakage occurs.

頁(從 - 到)10595-10599
期刊Journal of Physical Chemistry A
出版狀態已發佈 - 2000 十一月 1

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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