A dynamical test of the centroid formulation of quantum transition state theory for electron transfer reactions

✍ Scribed by C.H. Mak; John N. Gehlen

• Publisher: Elsevier Science
• Year: 1993
• Tongue: English
• Weight: 641 KB
• Volume: 206
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(93)85529-w

✦ Synopsis

Rigorous quantum dynamics simulations have been performed to test the path-integral centroid formulation proposed by Voth, Chandler and Miller for quanta1 rate constants in a simple class of models for electron transfer reactions in the tight-binding limit.

Fully dynamical quantum Monte Carlo simulations show that inside and slightly away from the diabatic limit the electron flux is invariant with the electronic centroid density near the dividing surface instead of being sharply peaked there. Despite this, we show analytically that the rate in this regime is largely governed by the ccntroid density on the dividing surface. But on approaching the adiabatic limit with larger electronic coupling, complex large-amplitude coherent oscillations develop in the quantum flux, suggesting that in addition to the imaginary-time centroid density, the dynamical factors also play an important role in determining the full quantal electron transfer rate.