CaltechAUTHORS
  A Caltech Library Service

Femtosecond real-time probing of reactions. 7. A quantum- and classical-mechanical study of the cyanogen iodide dissociation experiment

Roberts, Gareth and Zewail, Ahmed H. (1991) Femtosecond real-time probing of reactions. 7. A quantum- and classical-mechanical study of the cyanogen iodide dissociation experiment. Journal of Physical Chemistry, 95 (21). pp. 7973-7993. ISSN 0022-3654 . https://resolver.caltech.edu/CaltechAUTHORS:20160830-102556560

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20160830-102556560

Abstract

A comparison is presented between experiment and quantum and classical simulations of the time-dependent dynamics of the dissociation reaction of ICN via the A continuum. To illustrate the approach, second-order perturbation theory and a classical model (Ber. Bunsen-Ges. Phys. Chem. 1988, 92, 373) are employed to calculate the real-time behavior of dissociating [I⋅⋅⋅CN]^(••) species during the course of the reaction. In this way, the abilities of the two methods to describe accurately the reaction dynamics as revealed experimentally are evaluated: it is found that both quantum dynamical and classical mechanical treatments are capable of reproducing the essential temporal features probed by experiment and that, in this instance, classical equations of motion offer an adequate description of the process of nuclear separation. The difference between the relevant excited-state potential functions (over the long-range region) employed in the calculations is recovered from the simulated data by means of an inversion procedure (J. Chem. Phys. 1989, 90, 829) that relates absorption of the probing laser pulse to interfragment distance along the reaction coordinate. In addition, the variation in calculated transient behavior resulting from changes in the parameters describing the functional forms of the two potentials governing the observed reaction dynamics is examined in terms of their effect on characteristic reaction dissociation times, the lifetimes of transition-state configurations, and inversion to the difference between potential energy curves. Finally, comparison is made with analogous experimental and theoretical investigations of the fragmentation of the heavier Bi_2 molecule.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/j100174a002DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100174a002PublisherArticle
Additional Information:© 1991 American Chemical Society. Received: March 21, 1991. We are grateful to the National Science Foundation and Air Force Office of Scientific Research for financial support. G.R. thanks SERC for the award of a NATO Postdoctoral Fellowship, during the tenure of which this work was carried out. We also thank the referees for a thorough review of this manuscript and for useful suggestions.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Science and Engineering Research Council (SERC)UNSPECIFIED
North Atlantic Treaty Organization (NATO)UNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics8409
Issue or Number:21
Record Number:CaltechAUTHORS:20160830-102556560
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160830-102556560
Official Citation:Femtosecond real-time probing of reactions. 7. A quantum- and classical-mechanical study of the cyanogen iodide dissociation experiment Gareth Roberts and Ahmed H. Zewail The Journal of Physical Chemistry 1991 95 (21), 7973-7993 DOI: 10.1021/j100174a002
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70025
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:31 Aug 2016 17:15
Last Modified:03 Oct 2019 10:27

Repository Staff Only: item control page