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ADVANCES IN CHEMICAL PHYSICS
VOLUME 163
ADVANCES IN CHEMICAL
PHYSICS
VOLUME 163
Edited by
K. Birgitta Whaley
University of California,
Berkeley Palatine, United States
This edition first published 2018
© 2018 John Wiley & Sons, Inc.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or
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The right of K. Birgitta Whaley to be identified as the editor of this work has been asserted in
accordance with law.
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Library of Congress Catalog Number: 58-9935
ISBN: 9781119374992
Cover design by Wiley
Cover image: Courtesy of Hua Guo. Potential energy surfaces and wavefunctions involved in the
reaction dynamics of fluorine with water.
Set in 11/13pt, TimesLTStd by SPi Global, Chennai, India
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
EDITORIAL BOARD
Kurt Binder, Condensed Matter Theory Group, Institut Für Physik, Johannes
Gutenberg-Universität, Mainz, Germany
William T. Coffey, Department of Electronic and Electrical Engineering, Print-
ing House, Trinity College, Dublin, Ireland
Karl F. Freed, Department of Chemistry, James Franck Institute, University of
Chicago, Chicago, IL, USA
Daan Frenkel, Department of Chemistry, Trinity College, University of Cam-
bridge, Cambridge, UK
Pierre Gaspard, Center for Nonlinear Phenomena and Complex Systems, Uni-
versité Libre de Bruxelles, Brussels, Belgium
Martin Gruebele, Departments of Physics and Chemistry, Center for
Biophysics and Computational Biology, University of Illinois at
Urbana-Champaign, Urbana, IL, USA
Gerhard Hummer, Theoretical Biophysics Section, NIDDK-National Institutes
of Health, Bethesda, MD, USA
Ronnie Kosloff, Department of Physical Chemistry, Institute of Chemistry, Fritz
Haber Center for Molecular Dynamics, The Hebrew University of Jerusalem,
Jerusalem, Israel
Ka Yee Lee, Department of Chemistry, James Franck Institute, University of
Chicago, Chicago, IL, USA
Todd J. Martinez, Department of Chemistry, Photon Science, Stanford Univer-
sity, Stanford, CA, USA
Shaul Mukamel, Department of Chemistry, School of Physical Sciences, Uni-
versity of California, Irvine, CA, USA
Jose N. Onuchic, Department of Physics, Center for Theoretical Biological
Physics, Rice University, Houston, TX, USA
Stephen Quake, Department of Bioengineering, Stanford University, Palo Alto,
CA, USA
Mark Ratner, Department of Chemistry, Northwestern University, Evanston, IL,
USA
David Reichman, Department of Chemistry, Columbia University, New York
City, NY, USA
George Schatz, Department of Chemistry, Northwestern University, Evanston,
IL, USA
Steven J. Sibener, Department of Chemistry, James Franck Institute, University
of Chicago, Chicago, IL, USA
Andrei Tokmakoff, Department of Chemistry, James Franck Institute, Univer-
sity of Chicago, Chicago, IL, USA
Donald G. Truhlar, Department of Chemistry, University of Minnesota,
Minneapolis, MN, USA
John C. Tully, Department of Chemistry, Yale University, New Haven, CT, USA
CONTENTS
ix
x LIST OF CONTRIBUTORS VOLUME 163
K. Birgitta Whaley
Department of Chemistry
The University of California, Berkeley
PREFACE TO THE SERIES
Stuart A. Rice
Aaron R. Dinner
July 2017, Chicago, IL, USA
xiii
APPLICATIONS OF QUANTUM STATISTICAL
METHODS TO THE TREATMENT OF
COLLISIONS
1
Department of Chemistry, The Johns Hopkins University, Baltimore,
MD 21218-2685, USA
2
Department of Chemistry and Biochemistry, Institute for Physical
Science and Technology, University of Maryland, College Park,
MD 20741-2021, USA
CONTENTS
I. Introduction
II. Quantum Statistical Theory
III. Fine-Structure Branching in Reactive O(1 D) + H2 Dynamics
IV. Inelastic OH + H Collisions
A. OH + H Vibrational Relaxation
B. OH + D Isotope Exchange
C. OH + H Rotationally Inelastic Collisions
V. OH + O Reaction and Vibrational Relaxation
VI. Inelastic Collisions of the CH Radical
A. CH + H2
B. CH + H
VII. H + O2 Transport Properties
VIII. Conclusion
Acknowledgments
References
I. INTRODUCTION
Advances in Chemical Physics, Volume 163, First Edition. Edited by K. Birgitta Whaley.
© 2018 John Wiley & Sons, Inc. Published 2018 by John Wiley & Sons, Inc.
1
2 PAUL J. DAGDIGIAN and MILLARD H. ALEXANDER
of electronically excited atoms with H2 [C(1 D), N(2 D), O(1 D), and S(1 D),
for instance]. Here, atom M inserts into the H−H bond with the subse-
quent formation of a transient HMH complex, which then decays to form
MH + H products.
Statistical models for reactions involving the formation and decay of
a complex were first proposed in the 1950s to describe nuclear collisions
[3]. These models were then applied to molecular collisions [4]. Molecular
statistical theories were put on a firm theoretical footing by Miller [5], who
used as justification the formal theory of resonant collisions [6–8].
Pechukas and Light [9, 10] pioneered a statistical theory to predict the
rate and product internal state distribution of the reaction of an atom with
a diatomic molecule. This theory was based on Light’s work on the phase
space theory of chemical kinetics [11, 12] but, in addition, imposed detailed
balance. This work has formed the basis of modern quantum mechanical
treatments of complex-forming chemical reactions [13–17]. Here, once the
complex is formed, it can fall apart to yield any accessible reactant or prod-
uct subject to conservation of the total energy and angular momentum.
Pechukas and Light [9, 10] made some additional simplifications: First,
they assumed that the capture probability was zero or one, depending on
whether the reactants had sufficient energy to surmount the centrifugal
barrier for each partial wave (related to the total angular momentum J of
the collision complex). Second, they assumed that the long-range potential
could be described by an inverse power law, –C R−n . These assumptions,
particularly the latter, were reasonable in an era where calculation of a
potential energy surface (PES) was a major undertaking.
Subsequently, Clary and Henshaw [13] showed how to apply time-
independent (TID) coupled-states and close-coupling methods to the
determination of capture probabilities for systems with anisotropic long-
range interactions. More recently, Manolopoulos and coworkers [14, 15]
combined the statistical considerations of Pechukas and Light with the
Clary–Henshaw TID quantum capture probabilities, using, in addition,
accurate ab initio potential energy surfaces. This so-called “quantum
statistical” method has been applied to a number of atom–diatom reac-
tions that proceed through the formation and decay of a deeply bound
complex. Guo has demonstrated how a time-dependent (wavepacket, WP)
determination of the scattering wave function can be used in an equivalent
quantum-statistical investigation of reactions proceeding through deep
wells [18].
In related work, Quack and Troe [19] developed an adiabatic channel
model to describe the unimolecular decay of activated complexes.
APPLICATIONS OF QUANTUM STATISTICAL METHODS 3
1
Aʺ
3Aʺ
3Aʺ
O(1D) + H2
O(3P) + H2
OH + H
H2O(1Aʹ)
Figure 1. Schematic diagram of the potential energy surfaces of the OHH system. Only
the lowest (1 A′ ) PES was taken into account in the initial quantum statistical calculations
on the O(1 D) + H2 reaction [14, 15]. Note that H2 O (1 A′ ) well lies ≈ 59,000 cm−1 below
the O(1 D) + H2 asymptote. Adapted from Rackham et al. 2001 [14] and Rackham et al.
2003 [15].
4 PAUL J. DAGDIGIAN and MILLARD H. ALEXANDER
with energy below the O(1 D)+H2 asymptote. And this does not include
rotational levels. Thus, full quantum reactive scattering calculations for
complex-mediated reactions are a heroic task [23].
In the quantum statistical method, the close-coupled scattering
equations are solved outside of a minimum approach distance, the
“capture radius” RC , at which point the number of energetically accessible
states (open channels) is much less than at the minimum of the ABC†
complex. Also, because the point of capture occurs well out in the
reactant and/or product arrangement, one does not need to consider the
mathematical and coding complexities associated with the transformation
from the reactant to product states [24]. It is these simplifications that
make the quantum statistical method so attractive.
Formation of a transient complex does not always lead to chem-
ical reaction. The complex may decay to the reactant arrangement,
resulting in an inelastic collision. The present review outlines the appli-
cation of quantum statistical theory to nominally nonreactive collisions
that access PESs having one or more deep wells. Consider, the generic
A + BC → ABC† → AB + C collision. The inelastic event A + BC(v, j) →
A + BC(v′ , j′ ) can occur in a direct (non-complex-forming) collision,
either through an encounter in which the partners approach in a repulsive
geometry or at a larger impact parameter, where the centrifugal barrier
prevents access to the complex. In addition, complex formation (ABC† )
and subsequent decay into the reactant arrangement will also contribute
to inelasticity.
In general, weak, glancing collisions contribute substantially to rota-
tional inelasticity. Thus, one might naively expect that both direct and
complex-forming processes will contribute to rotational inelasticity. By
contrast, vibrational inelasticity in collisions on basically repulsive PESs
is very inefficient [25, 26], because the variation of repulsive PESs with
the vibrational modes of the molecular moiety is weak. Thus, one might
anticipate that the formation of a transient complex, in which substantial
change in the bond distances might occur, could make a major contribution
to vibrational relaxation.
Also, for A + BC collision systems where one of the reactants is an
open-shell species, typically (as shown schematically in Fig. 1), there
are a number of electronic states that correlate with the A + BC (or
AB + C) asymptote. Of these states, one (or, only a few) leads to strongly
bound ABC† intermediates, while the others are repulsive. The branching
between the energetically accessible fine-structure levels of the products
(in the case of OH, the spin–orbit and Λ-doublet levels) will be controlled
by the coupling between the various electronic states as they coalesce in
APPLICATIONS OF QUANTUM STATISTICAL METHODS 5
In Eq. (2), Ei is the internal energy of the initial level pair, 𝜇 is the collision
reduced mass, J is the total angular momentum, L and L′ are the initial and
APPLICATIONS OF QUANTUM STATISTICAL METHODS 17
4 F1 Aʹ
3
State-to-state cross sections (Å2)
Aʺ
2
2.5
2 F2 Aʹ
1.5
Aʺ
1
1.5
0
0.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5
jʹ