Classical and quantum reaction probabilities and thermal rate constants for the collinear H+H2 exchange reaction with vibrational excitation

✍ Scribed by J.M. Bowman; A. Kuppermann

• Publisher: Elsevier Science
• Year: 1971
• Tongue: English
• Weight: 409 KB
• Volume: 12
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(71)80602-4

✦ Synopsis

Ck~sical trajectory cakuk~tions for the collinea_r H+H2 exchange reaction weie performed QSiIIg the same poten-.

I&J merg

surface pretiou+ly adopted for exact quantum mechanical calculationr Reactions of bath sound state amjv-ibrationdy excited aate reagent were wwidered, over a relative kinetic energy range sufficient to produce vibrational excitation of products, At energies dose to threshold the dassicd and quaiimm IIICC~IZJ-G~ ICC&~ p-badiEties differ sufficiently to cause a major difference in the conzsponding thermal rate constants at IJW temperatures. Effective reaction thresholds differ by 0.07 eV for ground state and 0.09 eV for excited state reagent At energies substantially above threshold the quantum reaction probabilitieioscillate around the corresponding classica cries. However, some classical curves also show oscillatory behavior, suggesting caution ii~ the assignment of bscillations in the qrantuncurves to quantum effects.