Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

Nonstatistical dynamics on the caldera

Collins, Peter, Kramer, Zeb C., Carpenter, Barry K., Ezra, Gregory S. and Wiggins, Stephen 2014. Nonstatistical dynamics on the caldera. Journal of Chemical Physics 141 (3) , 034111. 10.1063/1.4889780

Full text not available from this repository.

Abstract

We explore both classical and quantum dynamics of a model potential exhibiting a caldera: that is, a shallow potential well with two pairs of symmetry related index one saddles associated with entrance/exit channels. Classical trajectory simulations at several different energies confirm the existence of the “dynamical matching” phenomenon originally proposed by Carpenter, where the momentum direction associated with an incoming trajectory initiated at a high energy saddle point determines to a considerable extent the outcome of the reaction (passage through the diametrically opposing exit channel). By studying a “stretched” version of the caldera model, we have uncovered a generalized dynamical matching: bundles of trajectories can reflect off a hard potential wall so as to end up exiting predominantly through the transition state opposite the reflection point. We also investigate the effects of dissipation on the classical dynamics. In addition to classical trajectory studies, we examine the dynamics of quantum wave packets on the caldera potential (stretched and unstretched). These computations reveal a quantum mechanical analogue of the “dynamical matching” phenomenon, where the initial expectation value of the momentum direction for the wave packet determines the exit channel through which most of the probability density passes to product.

Item Type: Article
Date Type: Published Online
Status: Published
Schools: Advanced Research Computing @ Cardiff (ARCCA)
Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Institute of Physics
ISSN: 0021-9606
Funders: EPSRC, NSF
Last Modified: 18 Feb 2019 13:16
URI: http://orca.cf.ac.uk/id/eprint/61989

Citation Data

Cited 20 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item Edit Item