Supercomputer Algorithms for Reactivity, Dynamics and Kinetics of Small Molecules

435 Pages·1989·14.678 MB·English

by  Charles W. Bauschlicher Jr. (auth.), Antonio Laganà (eds.)

Supercomputer Algorithms for Reactivity,
Dynamics and Kinetics of Small Molecules
NATO ASI Series
Advanced Science Institutes Series
A Series presenting the results of activities sponsored by the NA TO Science Committee,
which aims at the dissemination of advanced scientific and technological knowledge,
with a view to strengthening links between scientHic communities.
The Series is published by an international board of publishers in conjunction with the
NATO Scientific Affairs Division
A Llf. Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical Kluwer Academic Publishers
and Physical Sciences Dordrecht, Boston and London
D Behavioural and Social Sciences
E Applied Science.
F Computer and Systems Sciences Springer-Verlag
G Ecological Sciences Berlin, Heidelberg, New York, London,
H Cell Biology Paris and Tokyo
Series C: Mathematical and Physical Sciences -Vol. 277
Supercomputer Algorithms for
Reactivity, Dynamics and Kinetics
of Small Molecules
edited by
Antonio Lagana
Department of Chemistry,
University of Perugia,
Perugia, Italy
Kluwer Academic Publishers
Dordrecht / Boston / London
Published in cooperation with NATO Scientific Affairs Division
Proceedings of the NATO Advanced Research Workshop on
Supercomputer Algorithms for Reactivity, Dynamics and Kinetics of Small Molecules
Colombella di Perugia, Italy
30 August - 3 September 1988
Library of Congre. cataloging In Publication Data
NATO Advanced Research Workshop on ·Supercoaputer Algorlthas for
ReactIvIty, DynamIcs, and KInetIcs of Saall Molecules· (1988:
Coloabella, Italy)
Supercoaputer algorlthas for reactIvIty, dynamIcs, and kInetIcs of
small molecules: proceedIngs of the NATO Advanced Research Workshop
on ·Supercomputer AlgorIthms for ReactIvIty, Dynaalcs, and KInetIcs
of Saall Molecules,· held In Coloabella dl Perugla, Italy, 30
August-3 Septeaber 1988 I edIted by AntonIo Lagana.
p. ca. -- (NATO ASI serIes. SerIes C, Matheaatlcal and
physIcal scIences: vol. 277)
Includes Index.
ISBN-13: 978-94-010-6915-1
1. ReactIvIty (Chealstry)--Data processlng--Congresses.
2. Chealcal reactIon, Rate of--Data processlng--Congresses.
3. Molecular dynaalcs--Data processlng--Congresses.
4. Supercoaputers--Congresses. I. Lagana, AntonIo. II. TItle.
III. SerIes: NATO ASI serIes. SerIes C, Matheaatlcal and physIcal
scIences: no. 277.
00505.5. N37 1988
541.3'94'0285--dc19 89-2457
ISBN-13: 978-94-010-6915-1 e-ISBN-13:978-94-009-0945-8
DOl: 10.1007/978-94-009-0945-8
Published by Kluwer Academic Publishers,
P.O. Box 17, 3300 AA Dordrecht, The Netherlands.
Kluwer Academic Publishers incorporates the publishing programmes of
D. Reidel, Martinus Nijhoff, Dr W. Junk and MTP Press.
Sold and distributed in the U.S.A. and Canada
by Kluwer Academic Publishers,
101 Philip Drive, Norwell, MA 02061, U.S.A.
In all other countries, sold and distributed
by Kluwer Academic Publishers Group,
P.O. Box 322,3300 AH Dordrecht, The Netherlands.
Printed on acid free paper
All Rights Reserved
@ 1989 by Kluwer Academic Publishers
Softcover reprint of the hardcover 1st edition 1989
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical, including photo
copying, recording or by any information storage and retrieval system, without written
permission from the copyright owner.
Contents
Preface IX
RECENT ADVANCES IN ELECTRONIC STRUCTURE THEORY AND
THEIR INFLUENCE ON THE ACCURACY OF AB INITIO POTEN
TIAL ENERGY SURFACES
C.W. Bauschlicher, Jr., S.R. Langhoff, and P.R. Taylor 1
MODERN ELECTRONIC STRUCTURE CALCULATIONS: THE ACCU
RATE PREDICTION OF SPECTROSCOPIC BAND ORIGINS
N.C. Handy 23
POTENTIAL ENERGY SURFACES OF SEVERAL ELEMENTARY
CHEMICAL REACTIONS
K. Morokuma, K. Yamashita, and S. Yabushita 37
CALCULATION AND CHARACTERIZATION OF REACTION VAL
LEYS FOR CHEMICAL REACTIONS
T.H. Dunning, Jr., L.B. Harding, and E. Kraka 57
COMPUTED POTENTIAL ENERGY SURFACES FOR CHEMICAL RE
ACTIONS
S.P. Walch, and C. McMichael Rohlfing 73
AN AB INITIO STUDY ON THE COORDINATION OF FORM
ALDEHYDE, CARBON DIOXIDE, DINITROGEN AND RELATED
;\10LECULES TO IRON(O) AND NICKEL(O) FRAGMENTS
M. Rosi, A. Sgamellotti, F. Tarantelli, and C. Floriani 85
KINETIC PATHS FROM THE HYPERSPHERICAL PERSPECTIVE: AB
INITIO POTENTIAL ENERGY SURFACE FOR THE 0(3 P)+ H2 REAC
TION
V. Aquilanti, S. Cavalli, G. Grossi, M. Rosi, A. Sgamellotti, and F. Tarantelli 95
EXACT QUANTUM RESULTS FOR REACTIVE SCATTERING USING
HYPERSPHERICAL (APH) COORDINATES
G.A. Parker, R.T Pack, A. Lagana., B.J. Archer, J.D. Kress and Z. BaCic 105
COMPUTATIONAL STRATEGIES AND IMPROVEMENTS IN THE
LINEAR ALGEBRAIC VARIATIONAL APPROACH TO REARRANGE
MENT SCATTERING
D.W. Schwenke, M. Mladenovic, M. Zhao, D.G. Truhlar, Y. Sun and D.J.
Kouri 131
vi
HOW VARIATIONAL METHODS IN SCATTERING THEORY WORK
B. Ramachandran, and R.E. Wyatt 169
QUANTUM DYNAMICS OF SMALL SYSTEMS USING DISCRETE
VARIABLE REPRESENTATIONS
J.C. Light, R.M. Whitnell, T.J. Park, and S.E. Choi 187
FINITE ELEMENT CALCULATIONS OF SCATTERING MATRICES
FOR ATOM-DIATOM REACTIVE COLLISIONS. EXPERIENCES ON
AN ALLIANT FX/8
J. Linderberg 215
INVESTIGATIONS WITH THE FINITE ELEMENT METHOD. THE
COLLINEAR H + H2, F + H2 AND N e + Hi REACTIONS
R. Jaquet 223
CALCULATION OF MULTICHANNEL EIGENVALUES AND RESO
NANCES
R.W. Anderson 235
ACCURATE DETERMINATION OF POLYATOMIC INFRARED SPEC
TRA
C. lung, and C. Leforestier 251
THE CALCULATION OF RO-VIBRATIONAL SPECTRA USING SU
PERCOMPUTERS
J. Tennyson, S. Miller, and B.T. Sutcliffe 261
APPROXIMATE QUANTUM TECHNIQUES FOR ATOM DIATOM RE
ACTIONS
A. Lagana., E. Garcia, and O. Gervasi 271
APPROXIMATE QUANTUM MECHANICAL CALCULATIONS ON
MOLECULAR ENERGY TRANSFER AND PREDISSOCIATION
D.C. Clary 295
TEMPERATURE-DEPENDENT RATE CONSTANTS FOR
+
ION-DIPOLE REACTIONS: C+e P) HCI(XIE+)
C.E. Dateo, and D.C. Clary 327
CLASSICAL PATH APPROACH TO INELASTIC AND REACTIVE
SCATTERING
G.D. Billing 339
INTRAMOLECULAR ENERGY TRANSFER IN HC and HO OVER-
TONE EXCITED MOLECULES
J. Santamar{a, A. Garcia Ayllon, C. Getino, and P.A. Enr{quez 357
vii
CLASSICAL TRAJECTORY STUDIES OF GAS PHASE REACTION DY
NAMICS AND KINETICS USING AD INITIO POTENTIAL ENERGY
SURFACES
R.L. Jaffe, M.D. Pattengill, and D.W. Schwenke 367
QUASICLASSICAL CALCULATIONS FOR ALKALI AND ALKALINE
EARTH + HYDROGEN HALIDE CHEMICAL REACTIONS USING SU
PERCOMPUTERS
J .M. Alvariiio, E. Garcia, and A. Lagana. 383
DYNAMICS OF THE LIGHT ATOM TRANSFER REACTION: Cl +
HC1-+ C1H + Cl
J.N.L. Connor, and W. Jakubetz 395
THE MODELING OF COMPLEX GAS PHASE REACTIONS: FROM EX
PERT SYSTEMS TO SUPERCOMPUTERS
G.M. Come, and G. Scacchi 413
Index 433
Preface
The need for accurate computational procedures to evaluate detailed properties of gas
phase chemical reactions is evident when one considers the wealth of information provided
by laser, molecular beam and fast How experiments. By stressing ordinary scalar computers
to their limiting performance quantum chemistry codes can already provide sufficiently
accurate estimates of the stability of several small molecules and of the reactivity of a few
elementary processes. However, the accurate characterization of a reactive process, even
for small systems, is so demanding in terms of computer resources to make the use of
supercomputers having vector and parallel features unavoidable.
Sometimes to take full advantage from these features all is needed is a restructure of
those parts of the computer code which perform vector and matrix manipulations and a
parallel execution of its independent tasks. More often, a deeper restructure has to be
carried out. This may involve the problem of choosing a suitable computational strategy
or the more radical alternative of changing the theoretical treatment. There are cases, in
fact, where theoretical approaches found to be inefficient on a scalar computer exhibit their
full computational strength on a supercomputer.
The discussion at the NATO workshop" Supercomputer Algorithm6 for Reactivity, Dy
namic6 and Kinetic6 oj. 6mall Molecule6" held by the end of August 1988 at the Villa
Colomb ella, (Colombella di Perugia, Italy) has focussed upon these aspects. This book
collects the papers of both invited and contributed lectures. The first part of the book
deals with supercomputer strategies for the calculation of the electronic structure of small
molecules and the investigation of potential energy features characterizing a reactive pro
cess. In the second part theoretical methods developed for the exact calculation of the
dynamics of reactive atom diatom systems are described. Finally, in the last section, quan
tum reduced dimensionality as well as classical three dimensional (including semiclassical
corrections) approaches are discussed for extension to more complex systems. Applications
of artificial intelligence techniques are also presented. In all papers particular attention has
been given to storage management and speed up problems related to the use of vector and
parallel features.
The book shows how intense has been in recent years the work for designing parallel and
vector algorithms. Accurate electronic structure of reactive systems as well as exact and
high level approximate three-dimensional calculations of the reactive dynamics, efficient
directive and declaratory software for modeling complex systems. In turn, new and more
complex problems have been posed by these advances. Some of them are concerned with
the definition of the computer architecture better suited for chemical calculations. Others
are concerned with balancing within the application vector and parallel structures.
The workshop has been generously funded by the Scientific Affairs Division of NATO.
Antonio Lagana
Department of Chemistry
University of Perugia, Italy
ix
RECENT ADVANCES IN ELECTRONIC STRUCTURE THEORY
AND THEIR INFLUENCE ON THE ACCURACY OF AB INITIO
POTENTIAL ENERGY SURFACES
Charles W. Bauschlicher, Jr., Stephen R. Langhoff
NASA Ames Research Center
Moffett Field, CA 94035
and
Peter R. Taylor
ELORET Institute
Sunnyvale, CA 94087
ABSTRACT. Recent advances in electronic structure theory and the availability
of high speed vector processors have substantially increased the accuracy of ab
initio potential energy surfaces. The recently developed atomic natural orbital
approach for basis set contraction has reduced both the basis set incompleteness and
superposition errors in molecular calculations. Furthermore, full CI calculations can
often be used to calibrate a CASSCF /MRCI approach that quantitatively accounts
for the valence correlation energy. These computational advances also provide a
vehicle for systematically improving the calculations and for estimating the residual
error in the calculations. Calculations on selected diatomic and triatomic systems
will be used to illustrate the accuracy that currently can be achieved for molecular
systems. In particular, the F+H2 ---+HF+H potential energy hypersurface is used to
illustrate the impact of these computational advances on the calculation of potential
energy surfaces.
I. INTRODUCTION
The theoretical determination of purely ab initio reaction rates is becoming
an important area of computational chemistry research. At NASA Ames Research
Center there is considerable interest in determining rates for chemical reactions
occuring at high temperatures and in exotic environments. These conditions will
be encountered in the re-entry bow shock wave of aero-assisted orbital transfer
vehicles (AOTV) [1] or inside the combustion chamber of the hydrogen-fuelled hy
personic craft National Aero-space Plane (NASP) [2]. It is important to have such
rate data at the design stage in order to estimate what heating effects will be en
countered during re-entry and the combustion efficiency that can be expected under
hypersonic conditions. However, it is clearly very difficult (sometimes it is not even
possible) to study such environments in the laboratory, and as a result theoretical
determinations can provide data that is simply not obtainable by other means.
At present, there is a variety of methodologies [3] for carrying out calculations
of reaction cross sections, rate constants and product state distributions. In general,
these dynamical methods, either classical or quantum mechanical, are based on
knowledge of the potential energy surface (PES), and as a result, the accuracy of the
kinetic predictions ultimately depends on the PES itself. Futher, those dynamical
A. Lagana (ed.). Supercomputer Algorithms for Reactivity. Dynamics and Kinetics ofS mall Molecules. 1-21.
@ 1989 by Kluwer AcademU: Publishers.
2
methods which rely on a global representation of the PES are conditioned not only
by the accuracy of the computed energy points, but also by the techniques used to
represents these points with a functional form.
In the present work we shall discuss recent advances in quantum chemical
methodology that have improved the reliability of ab initio electronic structure cal
culations. These include full configuration interaction (FCI) calculation2s [4-13],
which have given new insight into the errors associated with the common prox
imations for treating electron correlation, and atomic natural orbital (ANO basis
sets [14-15], which have reduced the error in the one-particle basis sets by owing
large primitive sets to be contracted with little loss in accuracy. In cases for which
it would be unreasonably expensive to apply these techniques over the whole PES,
we demonstrate that it should be possible to study the global surface by adjusting
a PES based on a lower (and less expensive) level of theory using very accurate
calculations performed at the critical points of the surface. It is hoped that surfaces
generated in this manner will be sufficiently accurate that comparison with experi
ment will provide insight into the limitations of the dynamical studies rather than
reflect the limitations of the PES itself. This, of course, presupposes that adequate
methods for fitting the computed energy points are available [16]; this aspect of the
problem is discussed briefly below, but is generally beyond the scope of the present
work.
In Section II we give an overview of current theoretical methods. It is not our
aim to provide detailed descriptions of methods and algorithms, but rather to discuss
the techniques used in broad terms for reference in later discussions. In Sections III
and IV we discuss FCI calibration calculations and ANO basis sets, respectively.
In Section V, the accuracy of current methods is illustrated by comparing with
selected diatomic and triatomic systems where accurate experimental spectroscopic
constants are available for comparison. We consider the F+H2 ~FH+H reaction
in Section VI, and Section VII contains our conclusions.
II. QUANTUM CHEMICAL METHODOLOGY
The determination of a PES to be used in computing reaction rates involves
solving the non-relativistic time-independent Schrodinger equation for fixed nuclear
positions in the Born-Oppenheimer approximation. A review of the general method
ology of computational chemistry is given in Ref. 17. The first step in solving the
Schrodinger equation is to select a one-particle basis set. This is generally a set of
Gaussian-type orbitals (GTOs), grouped into fixed linear combinations called con
tracted functions. While this type of one-particle basis is universally referred to as
an atomic orbital basis, it must be borne in mind that the description it provides
of the individual atoms is often far from perfect. This can lead to problems in de
scribing atom-atom interactions or binding, since deficiencies in the "atomic basis"
for one atom can be compensated for by using part of the basis on another center,
resulting in a completely spurious energy lowering referred to as superposition er
ror (SE) [18]. The effects of superposition error on a computed PES are discussed
in more detail below.
Once the one-particle basis has been chosen, a method for solving for the elec
tronic motion must be selected. In principle, the correlation, or n-particle, problem
can be solved exactly in a given one-particle basis set by a full configuration inter
action (FCI) calculation, which includes all arrangements of the n electrons in the
given one-particle basis, consistent with Fermi statistics and the desired spin and
spatial symmetry. However, the length of the FCI expansion increases factorially