TY - JOUR
T1 - Monoenergetic unimolecular rate constants and their dependence on pressure and fluctuations in state-specific unimolecular rate constants
AU - Lu, Da Hong
AU - Hase, William L.
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 1989
Y1 - 1989
N2 - The Porter-Thomas distribution function P(k) is used to represent fluctuations in state-specific unimolecular rate constants for states that lie within a narrow energy interval E → E + dE. The sensitivity of concentration of reactant molecules versus time N(τ,E), the time-dependent rate constant k(τ,E), and the collision-averaged rate constant k(ω,E) to the width of P(k) is considered. The collision-averaged rate constant k(ω,E), found from an analysis of a Stern-Volmer plot, is found to be rather insensitive to P(k).
AB - The Porter-Thomas distribution function P(k) is used to represent fluctuations in state-specific unimolecular rate constants for states that lie within a narrow energy interval E → E + dE. The sensitivity of concentration of reactant molecules versus time N(τ,E), the time-dependent rate constant k(τ,E), and the collision-averaged rate constant k(ω,E) to the width of P(k) is considered. The collision-averaged rate constant k(ω,E), found from an analysis of a Stern-Volmer plot, is found to be rather insensitive to P(k).
UR - http://www.scopus.com/inward/record.url?scp=0011713112&partnerID=8YFLogxK
U2 - 10.1021/j100342a002
DO - 10.1021/j100342a002
M3 - Article
AN - SCOPUS:0011713112
VL - 93
SP - 1681
EP - 1683
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 5
ER -