TY - JOUR
T1 - Role of angular momentum in statistical unimolecular rate theory
AU - Aubanel, Eric E.
AU - Wardlaw, David M.
AU - Zhu, Ling
AU - Hase, William L.
N1 - Funding Information:
This research was supported by the National Science Foundation of the United States and the Natural Sciences and Engineering Research Council (NSERC) of Canada. D.M.W. is a University Research Fellow of NSERC.
PY - 1991
Y1 - 1991
N2 - A variety of topics is reviewed with an emphasis on assessment of models and discussion of their underlying physical assumptions, rather than on an overview of applications. Different treatments of angular momentum in the Rice-Ramsperger-Kassel-Marcus theory are surveyed and compared for tight and flexible transition states. The influence of angular momentum on thermal reaction rates is examined within the framework of variational transition state theory. The vibrational/rotational adiabatic theory of unimolecular decomposition is discussed. Various models for product energy distributions are summarized. The nature of nonthermal distributions of reactant angular momentum, arising from particular experimental techniques, is examined. A brief discussion of theoretical studies of vibrational/rotational coupling in the reactant and at the transition state is provided. The review attempts to unify advances in the fields of neutral and ion unimolecular decomposition.
AB - A variety of topics is reviewed with an emphasis on assessment of models and discussion of their underlying physical assumptions, rather than on an overview of applications. Different treatments of angular momentum in the Rice-Ramsperger-Kassel-Marcus theory are surveyed and compared for tight and flexible transition states. The influence of angular momentum on thermal reaction rates is examined within the framework of variational transition state theory. The vibrational/rotational adiabatic theory of unimolecular decomposition is discussed. Various models for product energy distributions are summarized. The nature of nonthermal distributions of reactant angular momentum, arising from particular experimental techniques, is examined. A brief discussion of theoretical studies of vibrational/rotational coupling in the reactant and at the transition state is provided. The review attempts to unify advances in the fields of neutral and ion unimolecular decomposition.
UR - http://www.scopus.com/inward/record.url?scp=0000195172&partnerID=8YFLogxK
U2 - 10.1080/01442359109353259
DO - 10.1080/01442359109353259
M3 - Article
AN - SCOPUS:0000195172
VL - 10
SP - 249
EP - 286
JO - International Reviews in Physical Chemistry
JF - International Reviews in Physical Chemistry
SN - 0144-235X
IS - 3
ER -