Issue 1, 2010

Quasi-classical statistico-dynamical description of polyatomic photo-dissociations: state-resolved distributions

Abstract

An alternative methodology to investigate indirect polyatomic processes with quasi-classical trajectories is proposed, which effectively avoids any binning or weighting procedure while provides rovibrational resolution. Initial classical states are started in terms of angle-action variables to closely match the quantum experimental conditions and later transformed into Cartesian coordinates, following an algorithm very recently published [J. Chem. Phys. 2009, 130, 114103]. Trajectories are then propagated using the ‘association’ picture, i.e. an inverse dynamics simulation in the spirit of the exit-channel corrected phase space theory of Hamilton and Brumer [J. Chem. Phys. 1985, 82, 595], which is shown to be particularly convenient. Finally, an approximate quasi-classical formula is provided which under general conditions can be used to add possible rotational structures into the vibrationally-resolved quasi-classical distributions. To introduce the method and illustrate its capabilities, correlated translational energy distributions from recent experiments in the photo-dissociation of ketene at 308 nm [J. Chem. Phys. 2006, 124, 014303] are investigated. Quite generally, the overall theoretical algorithm reduces the total number of trajectories to integrate and allows for fully theoretical predictions of experiments on polyatomics.

Graphical abstract: Quasi-classical statistico-dynamical description of polyatomic photo-dissociations: state-resolved distributions

Article information

Article type
Paper
Submitted
22 Aug 2009
Accepted
07 Oct 2009
First published
10 Nov 2009

Phys. Chem. Chem. Phys., 2010,12, 115-122

Quasi-classical statistico-dynamical description of polyatomic photo-dissociations: state-resolved distributions

M. L. González-Martínez, L. Bonnet, P. Larrégaray and J. Rayez, Phys. Chem. Chem. Phys., 2010, 12, 115 DOI: 10.1039/B917292K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements