Table of Contents
Laser Chemistry
Volume 2, Issue 5-6, Pages 253-269

Intramolecular Vibrational Relaxation in Electronically Excited States

1Université Louis Pasteur et Centre de Recherches Nucléaires, Strasbourg CEDEX 67037, France
2Department of Chemistry, Arizona State University, Tempe 85287, Arizona, USA

Copyright © 1983 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


A density matrix approach for describing intramolecular dynamics, with special application to vibrational relaxation in excited electronic states, is presented. We derive the master equations governing intramolecular transfer of excitation energy between the states in a zeroth-order basis defined by considering the excitation and detection conditions in the time-resolved experiments. It is shown that, in this formalism, the memory function plays a central role. We note that the form of intramolecular memory is determined by the importance of quantum mechanical mixing of the zeroth-order states. A distinction is made between the subsystems of states with strong and weak mixing properties; while the former account for quasiperiodic character of coherent motion, the latter display a Markovian behavior. The physical conditions fixing the relative importance of quasiperiodic and statistical dynamics in individual systems are discussed. In the application to time resolved intramolecular vibrational relaxation, special consideration is given to the nature of the initially excited doorway states and the intermode couplings. The symmetry restrictions and the possible role of rotational motion in vibrational relaxation are also discussed, before considering the recent results obtained by Zewail et al. with anthracene in the first excited singlet state.