On the unimolecular dissociation of large molecules

✍ Scribed by E.W. Schlag; R.D. Levine

• Publisher: Elsevier Science
• Year: 1989
• Tongue: English
• Weight: 673 KB
• Volume: 163
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(89)85180-2

✦ Synopsis

Large molecules excited to well above their dissociation threshold can still have a low mean energy per vibrational mode. The RRK statistical theory predicts rather long decay times for such activated molecules. Yet the dissociation of such molecules can be detected in a mass spectrometer, which requires lifetimes shorter than z 1O-6 s. Qualitative considerations of nonlinear dynamics suggest that the naive RRK theory may well not apply under such circumstances and that the Slater model (interpreted a 18 KAM), offers a better starting point. Limiting cases when the unimolecular decay rate can be far higher than that calculated by RRK theory for the full complement of degrees of freedom, are discussed.