Quantum photochemistry. Accurate quantum scattering calculations for an electronically nonadiabatic reaction

✍ Scribed by Steven L. Mielke; Gregory J. Tawa; Donald G. Truhlar; David W. Schwenke

• Publisher: Elsevier Science
• Year: 1995
• Tongue: English
• Weight: 456 KB
• Volume: 234
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(94)01515-w

✦ Synopsis

We present converged quantum mechanical scattering calculations of reaction and quenching probabilities for a problem involving an electronically excited product. The calculations correspond to two coupled potential energy surfaces representing the ground and first electronically excited state of H2Br. Results are presented for H + HBr ~ H 2 + Br and H + Br ~ H 2 + Br *, where an asterisk denotes electronic excitation, and the lack of an asterisk denotes the electronic ground state. The calculations are carried out by linear algebraic variational methods with a multi-arrangement diabatic basis. These benchmark calculations are used to test a one-dimensional model, which is found to be quantitatively unreliable.

Elsevier Science B.V. SSD! 0009-2614(94)01515-5

The present Letter reports such calculations 1 for the reaction H + HBr ~ H 2 + Br(2Pt/2), (I)

1 The results in the present Letter, as well as results for the reverse nonadiabatic reaction involving electronically excited reactants, were presented at the Workshop on Electronically Nonadiabatic Processes in Chemical Dynamics, Spectroscopy, and Electronic Structure, Argonne National Laboratory, July 20-23, 1994, and at the 208th ACS National Meeting, Washington, DC, August 21-25, 1994. In other papers at these meetings Schatz presented quantum dynamics calculations of transition probabilities for an electronically nonadiabatic model of the reaction of C1 with HCI', which provides another example of the advancing capabilities of current reactive scattering methods.