Dynamics of photoinduced reactions in hydrogen-bonded clusters: Classical studies of the photodissociation of (HCl)2

A. B. McCoy, Y. Hurwitz, R. B. Gerber*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

43 Scopus citations

Abstract

A theoretical investigation of the photodissociation dynamics of (HCl)2 at 193 nm is presented. Prior to excitation, the cluster is taken to be in its rotation-vibration ground state. A quantal description of this six-dimensional wave function is computed using diffusion quantum Monte Carlo (DQMC). The photodissociation dynamics are simulated by classical trajectories in which the molecule undergoes vertical excitation to an electronic state that is repulsive along one of the HCl stretch coordinates. The initial conditions for these trajectories are sampled according to the Wigner function which was obtained from the DQMC wave function. In a significant fraction of these trajectories, there is a reactive collision in which the H atom interacts with the H′Cl′ molecule to form HCl′. Of the remaining collisions, most are nonreactive, but a small number lead to H2 formation. The trajectories in which an exchange reaction occurs result typically in formation of HCl′ molecules that are rotationally and vibrationally hotter and in H atoms with lower kinetic energies than are found in the nonreactive trajectories. Resonances, in which the H atom undergoes multiple collisions with Cl and H′Cl′, are observed in all three classes of trajectories. The above results indicate that this is a rich system for the study of photoinduced chemical reactivity in hydrogen-bonded clusters.

Original languageEnglish
Pages (from-to)12516-12522
Number of pages7
JournalJournal of Physical Chemistry
Volume97
Issue number48
DOIs
StatePublished - 1993

Fingerprint

Dive into the research topics of 'Dynamics of photoinduced reactions in hydrogen-bonded clusters: Classical studies of the photodissociation of (HCl)2'. Together they form a unique fingerprint.

Cite this