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Books > Science & Mathematics > Chemistry > Physical chemistry > Quantum & theoretical chemistry
"The Theory of Atomic Spectra," surrrrnanzlllg all that was then
known about the quantum theory of free atoms; and in 1961, J.S.
Griffith published "The Theory of Transition Metal Ions," in which
he combined the ideas in Condon and Shortley's book with those of
Bethe, Schlapp, Penney and Van Vleck. All this work, however, was
done by physicists, and the results were reported in a way which
was more accessable to physicists than to chemists. In the
meantime, Carl J. Ballhausen had been studying quantum theory with
W. Moffitt at Harvard; and in 1962 (almost simultaneously with
Griffith) he published his extremely important book, "Introduction
to Ligand Field Theory." This influential book was written from the
standpoint of a chemist, and it became the standard work from which
chemists learned the quantum theory of transition metal complexes.
While it treated in detail the group theoretical aspects of crystal
field theory, Carl J. Ballhausen's book also emphasized the
limitations of the theory. As he pointed out, it is often not
sufficient to treat the central metal ion as free (apart from the
influence of the charges on the surrounding ligands): - In many
cases hybridization of metal and ligand orbitals is significant.
Thus, in general. a molecular orbital treatment is needed to
describe transition metal complexes. However, much of the group
theory developed In connection with crystal field theory can also
be used in the molecular orbital treatment.
Over the last twenty years, developments of the ab initio metho
dologies and of the computing capacities have progressively turned
quantum chemistry into a predictive tool for molecular systems
involving only light elements. The situation appears less advanced
for systems containing transition metal elements where specific
difficulties arise, like those 1inked to the quasi-degeneracy of
the lowest atomic states. Correlation effects, which are important
only for quantitative accuracy in the treatment of molecules made
of light elements, need sometimes to be considered even for a
qualitative des cription of transition metals systems (like the
multiple metal-metal bond). The treatment of atoms of a high atomic
number has necessited the development of model potential methods.
These difficulties ex acerbate for systems containing several trans
ition atoms a correct description of the dichromium molecule Crz
still represents a challenge to quantum chemists. Yet many advances
have been made recently in the theoretical treatment of these
systems, despite the fact that our understanding still remains
disparate with a variety of models and methodologies used more or
less successfully (one-electron models, explicitly correlated ab
initio methods, density functional formalisms). For these reasons,
a NATO Advanced Research Workshop was organized to review in detail
the state-of-the-art techniques and at the same time the most
common applications. These encompass many fields including the
spectroscopy of diatomics and small aggregates, structure and
reactivity problems in organometallic chemistry, the cluster
surface analogy with its implications for heterogeneous catalysis
and the description of extended structures."
The calculation of cross sections and rate constants for chemical
reactions in the gas phase has long been a major problem in
theoretical chemistry. The need for reliable and applicable
theories in this field is evident when one considers the
significant recent advances that have been made in developing
experimental techniques, such as lasers and molecular beams, to
probe the microscopic details of chemical reactions. For example,
it is now becoming possible to measure cross sections for chemical
reactions state selected in the vibrational rotational states of
both reactants and products. Furthermore, in areas such as
atmospheric, combustion and interstellar chemistry, there is an
urgent need for reliable reaction rate constant data over a range
of temperatures, and this information is often difficult to obtain
in experiments. The classical trajectory method can be applied
routinely to simple reactions, but this approach neglects important
quantum mechanical effects such as tunnelling and resonances. For
all these reasons, the quantum theory of reactive scattering is an
area that has received considerable attention recently. This book
describes the proceedings of a NATO Advanced Research Workshop held
at CECAM, Orsay, France in June, 1985. The Workshop concentrated on
a critical examination and discussion of the recent developments in
the theory of chemical reaction dynamics, with particular emphasis
on quantum theories. Several papers focus on exact theories for
reactions."
This treatment of molecular and atomic physics is primarily meant
as a textbook. It is intended for both chemists and physicists. *It
can be read without much knowledge of quantum mechanics or
mathematics, since all such details are explained-. It has
developed through a series of lectures at the Royal Institute of
Technology. The content is to about 50 % theoretical and to 50 %
experimental. The reason why the authors, who are experimentalists,
went into theory is the following. When we during the beginning of
the 1970's measured photo electron spectra of organic molecules, it
appeared to be impossible to understand them by use of available
theoretical calculations. To handle hydrocarbons we ( together with
C. Fridh ) constructed in 1972 a purely empirical procedure, SPINDO
[1] which has proved to be useful, but the extension to molecules
with hetero atoms appeared to be difficult. One of us ( L.A.)
proposed then another purely ~~E!E!~~! EE2~~~~E~ ( Hydrogenic Atoms
in Molecules, HAM/1, unpublished), in which the Fock matrix
elements f5..y were parametrized using Slater's shielding concept.
The self-repulsion was compensated by a term "-1". The
~~2~~_~ff2E~, HAM/2 [2] , started from the total energy E:. of the
molecule. The atomic parts of L used the Slater shielding
constants, and the bond parts of E. were taken from SPINDO. The
Fock matrix elements Fpv were then obtained from E in a
conventional way.
The development and computational implementation of analytical
expres sions for the low-order derivatives of electronic energy
surfaces and other molecular properties has undergone rapid growth
in recent years. It is now fairly routine for chemists to make use
of energy gradient information in locating and identifying stable
geometries and transition states. The use of second analytical
derivative (Hessian or curvature) expressions is not yet routine,
and third and higher energy derivatives as well as property (e.g.,
dipole moment, polarizability) derivatives are just beginning to be
applied to chemical problems. This NATO Advanced Research Workshop
focused on analyzing the re lative merits of various strategies for
deriving the requisite analyti cal expressions, for computing
necessary integral derivatives and wave function parameter
derivatives, and for efficiently coding these expres sions on
conventional scalar machines and vector-oriented computers. The
participant list contained many scientists who have been instrumen
tal in bringing this field to fruition as well as eminent
scientists who have broad knowledge and experience in quantum
chemistry in general."
In 1980. a distinguished group of scientists gathered In
Washington. D. C. for an International Symposium on Aging and
Cancer. Among the recommendations of this Symposium was to convene
a future meeting to discuss the molecular basis for
Interrelationships between aging and cancer when the appropriate
scientific knowledge was available. That same year. the 13th
Jerusalem Symposium on Quantum Chemistry and Biochemistry entitled
.Carcl nogenesls: Fundamental Mechanisms and Environmental
Effects.. was held. attended by some 50 International authorities
In this field. At this meeting. It became clear that the
fundamental process of carcinogenesis 15 Intimately associated with
differentiation. which must also be mechanistically related to
aging. It was therefore proposed that the next Jerusalem Symposium
on Cancer could provide the appropriate forum for the study on the
Interrelationship among cancer. aging and differentiation. The
Impressive advances In our knowledge of the nature of the genome
through molecular genetic and physical chemical techniques have now
provided the opportunity to examine the Interrelationships between
these complex biolo gical processes. Through the Isolation. cloning
and rearranging of genes we are able to dissect and manipulate the
genome In a fashion that was unanticipated only a decade ago. At
the same time. the Increase In longevity and the Increased numbers
of Individuals entering the last decades of life where cancer
Incidences are highest raise the profound and practical question of
whether aging and cancer are linked through common mechanisms."
At the American Chemical Society meeting in Philadelphia,
Pennsylvania, U.S.A., a symposium was organized entitled,
"Comparison of Ab Initio Quantum Chemistry with Experiment:
State-of-the-Art." The intent of the symposium was to bring
together forefront experimen talists, who perform the types of
clean, penetrating experiments that are amenable to thorough
theoretical analysis, with inventive theore ticians who have
developed high accuracy ab initio methods that are capable of
competing favorably with experiment, to assess the current
applicability of theoretical methods in chemistry. Contributions
from many of those speakers (see Appendix A) plus others selected
for their expertise in the subject are contained in this volume.
Such a book is especially timely, since with the recent develop
ment of new, more accurate and powerful ab initio methods coupled
with the exceptional progress achieved in computational equipment,
ab initio quantum chemistry is now often able to offer a third
voice to resolve experimental discrepancies, assist essentially in
the interpre tation of experiments, and frequently, provide
quantitatively accurate results for molecular properties that are
not available from experiment."
I get by with a little help from my friends The Beatles: Sgt.
Pepper This book should have been in Danish. Any decent person must
be able to express himself in his mother's tongue, also when
expounding scientific ideas and results. Had I stuck to this ideal,
the book would have been read by very few people, and, indeed,
appreciated by even fewer. Having it publ ished in English gives me
a chance to fulfill one ambition: to be read and judged by the
international scientific community. Another reason is that the
majority of my professional friends are regrettably unread in
Danish, just as I am in Hebrew, Finnish and even Italian. I want to
deprive them of the most obvious excuse for not reading my opus.
Like a man I admired, I will first of all thank my wife. In his
autobiography, Meir Weisgal, then President of the Weizmann Insti
tute of SCience, wrote about his wife: "In addition to her natural
endowments - which are considerable - she was a more than competent
part-tim secretary." He wrote on, and so shall I. The book has been
edited by my wife. So if the reader finds the layout pleasant as,
in actual fact, I myself do, Birgit is to be praised. If there are
blemishes, I am to be blamed for not having caught them."
Stereochemistry is the part of chemistry that relates observable
prop erties of chemical compounds to the structure of their
molecules, i. e. the relative spatial arrangement of their
constituent atoms. In classical stereochemistry, the spatial
arrangements relevant for interpreting and predicting a given
chemical property are customarily described by geometric features/
symmetries in some suitably chosen rigid model of the molecule The
solution of stereochemical problems involving single molecular
species is the danain of the geometry based approaches, such as the
methods of classical stereochemistry, molecular mechanics and
quantum chemistry. The molecules of a pure chemical compound form
generally an ensemble of molecular individuals that differ in
geometry and energy. Thus it is generally impossible to represent a
chemical compund adequately by the geo metry of a rigid molecular
model. In modern stereochemistry it is often necessary to analyze
molecular relation within ensembles and families of stereoisomers
and permutation isomers, including molecules whose geometric
features are changing with time. Accordingly, there is definitely a
need for new types of ideas, concepts, theories and techniques that
are usable beyond the scope of customary methodology. This is why
the present text was written."
The present Volume of Lecture Notes in Chemistry fulfils one of the
stated aims of the Series, that of disseminating results discussed
and evaluated at recent scientific international conferences; in
our case a Satellite Meeting of the well-known Conference Series on
the Physics of Electronic and Atomic a:ollisions, the XIIIth
ICPEAC, which took place in Castelgandolfo, near Rome, from 23 to
25 July 1983. Since the Satellite Meeting attracted a widely
international and in- terdisciplina~y audience whose general
consensus was one of warm appro- val for the scie'ntific level
achieved during it, we hope that the pre- sent collection of essays
will be met by similar success, thus warran- ting our having asked
the participants to work still further for us. Before turning to
their efforts, however, it is only just to thank the Italian
National Research Council (Chemistry Committee and Physics
Committee), the University of Rome, the C.N.R. Tnstitute H.A.I. of
the Rome Research Area (Montelibretti) and the E.N.E.A.
Organisation for their financial aid, which made the Castelgandolfo
Meeting possible. We warmly acknowledge the professional expertise
of the staff at Villa Montecucco and for their collaboration we are
grateful to: Rita Abbasciano, Catherine Cajone, Lucilla
Crescentini, .Roberta Fantoni, An- tonio Montani, Amedeo Palma,
Rosario Platania, Maurizio Venanzi.
At a time when computerized laboratory automation is producing a da
ta explosion, chemists are turning to applied mathematics and
statistics for the tools to extract useful chemical information
from data. This rush to find applicable methods has lead to a
somewhat confusing body of literature that represents a barrier to
chemists wishing to learn more about chemometrics. The confusion
results partly from the mixing of chemical notation and
nomenclature with those of statistics, applied mathematics and
engineering. Additionally, in the absence of collaboration with
mathematicians, chemists have, at times, misused data analysis
methodology and even reinvented methods that have seen years of
service in other fields. The Chemometrics Society has worked hard
to solve this problem since it was founded in 1974 with the goal of
improving communications between the chemical sciences and applied
mathe matics and statistics. The NATO Advanced Study Institute on
Chemometrics is evidence of this fact as it was initiated in
response to a call from its membership for advanced training in
several areas of chemometrics. This Institute focused on current
theory and application in the new field of Chemometrics: Use of
mathematical and statistical methods, Ca) to design or select
optimal measurement procedures and experiments; and Cb) to provide
maximum chemical information by analyzing chemical data. The
Institute had two formal themes and two informal themes."
The NATO Advanced Study Institute on "Quantum Chemistry of
Polymers; Solid State Aspects" lIIas held at the MARITIM Congress
Hotel Braunlage/Harz in the Federal Republic of Germany from July
25 - August 5, 1983. We lIIish to express our deep gratitude to the
NATO Scientific Affairs Division, the main sponsor of the
Institute, and to the National Foundation for Cancer Research,
Bethesda, Maryland for their substantial support. We sincerely
thank Dr. Craig Sinclair, Director of the NATO Advanced Study
Institutes program as lIIell as the IIIhole Advanced Study
Institute/Advanced Research Workshop Advisory Board of the NATO
Scientific Affairs Division, IIIho have honored us by holding their
external annual meeting during this School in Braunlage. We are
very much indebted also to Dr. Mario Di Lullo, Director of the
Advanced Research Workshop program of the NATO Scientific Affairs
Division IIIho together lIIith Dr. Sinclair has given a very
informative lecture about the NATO ASI/ARW programs. Special thanks
are due to Mr. Franklin Salisbury, Executive Director of the
National Foundation for Cancer Research, to Mrs. Tamara Salisbury,
Deputy Director of the National Foundation for Cancer Research and
to Dr. Mary Hennen Aldridge, President of the National Foundation
for Cancer Research, IIIho also honored the School lIIith their
presence.
The bond diagrammatic representation of molecules is the foundation
of MOVB theory. To a certain extent, this kind of representation is
analogous to the one on which "resonance theory" is based and this
fact can be projected by a comparison of the various ways in which
MOVB theory depicts a species made up of three core and two ligand
MO's which define two subsystems containing a total of six
electrons and the ways in which "resonance theory" (i. e. ,
qualitative VB theory) depicts a six-electron-six-AO species such
as the pi system of CH =CH-CH=CH-CH=O. The 2 different pictorial
representations are shown in Scheme 1 so that the analogies are
made evident. First of all, the total MOVB diagrammatic
representation of the 6/5 species is obtained by a linear
combination of three complete bond diagrams, as in Al, which
describe the optimal linear combination of!l! MOVB Configuration
Wavefunctions (CW's). By the same token, a total VB diagrammatic
representation of the 6/6 species can be obtained by writing a "dot
structure", as in Bl, and taking this to mean the optimal linear
combination of all VB CW's. Next, we can approxi mate the MOVB
wavefunction of the 6/5 species by one complete (or detailed) bond
dia gram" (A2). No simple VB representation analogy can be given in
this case. Alterna tively, we can approximate the MOVB wavefunction
by a linear combination of compact bond diagrams, as in A3, in the
way described before.
The Fourth International Congress in Quantum Chemistry under the
auspices of the International Academy of Molecular Quantum Science
in Menton, France was arranged at Uppsala University, Uppsala,
Sweden, during the period June 14 - 19, 1982, in close
collaboration with the University of Florida. The previous
congresses were held in Menton 1973, New Orleans 1976, and Kyoto
1979, and the 1985 congress is tentatively planned to be held in
the province of Quebec, Canada. The Congress consisted of six
symposia in various areas of quantum chemistry, solid-state theory,
and quantum bi ology. The meeting was attended by about 450
scientists from 45 different nations, and a total of more than 300
scientific papers were presented. Even the poster contri butions
were given some plenary time. These proceedings contain the text of
the plenary lec tures as well as the chairmen's introductions,
whereas the contributed papers will be published in the
International Journal of Quantum Chemistry, (John Wiley & Sons,
New York) in the regular January - April 1983 issues."
The Fifteenth Jerusalem Symposium reflected the high standards of
the former international scientific meetings, which convene once a
year at the Israel Academy of Sciences and Humanities in Jerusalem
to discuss a specific topic in the broad area of quantum chemistry
and biochemistry. The topic at this year's Jerusalem Symposium was
intramo lecular dynamics, a subject of central interest for
theoreticians, che mists and biologists. During the last two
decades, there has been remarkable pro gress in our understanding
of time dependent phenomena. The development and application of the
modern techniques of quantum mechanics and sta tistical mechanics
to excited-state dynamics and to chemical and biophy sical systems
constitutes a fast developing current research area. The main theme
of the Symposium was built around a conceptual framework for the
elucidation of photophysical and photochemical phenomena in atoms,
molecules, van der Waals complexes and clusters, condensed phases,
poly mers and biological supermolecules. The interdisciplinary
nature of this research field was deliberated by intensive and
extensive interactions between scientists from different
disciplines and between theory and experiment. This volume provides
a record of the invited lectures at the Symposium."
The aim of this chapter is to discuss in detail the Monte Carlo
algorithms developed to compute the sequence distributions in
polymers. Because stereoregular polymers constitute a unique form
of copolymer, the stereosequence distributions in vinyl
homopolymers and the sequence distributions in copolymers can be
computed using the same algorithms. Also included is a brief review
of probabilistic models (i. e. , Bernoulli trials and Markov
chains) frequently used to compute the sequence distribtuion. The
determination of sequence distributions is important for the under-
standing of polymer physical properties, to compute the monomer
reactivity para- meters and to discriminate among polymerization
mechanisms. 2. 2. Short review of analytical models, Monte Carlo
algorithms and computer programs. l A Bernoullian model was
developed by Price. Within this model the probability of a given
state of the system is independent of the previous state and does
not condition the next state. The Bernoullian behaviour has been
shown 24 to describe cls-trans distributions among 1, 4 additions
in polybutadienes - , 5 the comonomer distribution in
ethylene-vinyl acetate copolymer , and configura- 6 tional
distributions in polystyrene , poly (vinyl chloride)7, poly (vinyl
alcohol)7 Consider the binary copolymerization:;1,J=1,2 (1) where -
MI* , I = 1,2, is an ionic or radical polymeric chain end, and M, J
= 1,2, J is a monomer. Because the final state (i. e.
The third and last volume of this treatise IS concerned with
important applications of the quantum~theory of chemical reactions
to chemisorption, catalysis and biochemical reactions. The book
begins with an important paper devoted to the theoretical
background of heterogeneous catalysis. It is followed by two papers
showing typical applications of wave mechanics to the analysis of
chemisorption. Catalysed gas-solid reactions are chosen to
illustrate gas, organic solid state reaction and some aspects of
the mechanism of the FISCHER-TROPSCH synthesis are presented. The
second part of the book is devoted to biochemical applications of
quantum chemistry. Two papers are concerned with the quantum theory
of enzyme activity. Two others present recent progress of quantum
pharmacology. Finally an important contribution to the theory of
intermolecular forces is made in the view of possible applications
to biochemical problems. vii R. Daudel, A. Pullman, L. Salem, and
A. Viellard reds.), Quantum Theory o/Chemical Reactions, Volume
III, vii. Copyright (c) 1982 by D. Reidel Publishing Company.
THEORETICAL BACKGROUND OF HETEROGENEOUS CATALYSIS J.E.Germain
Laboratoire de Catalyse Appliquee et Cinetique Heterogene L. A. 231
du Centre National de la Recherche Scientifique Universite Claude
Bernard Lyon I, E.S.C.I.L. 43 Boulevard du 11 Novembre 1918, 69622
Villeurbanne Cedex. Heterogeneous Catalysis is a surface Kinetic
phenomenon by which a chemical reaction between molecules of a
fluid phase is accelerated (activity) and oriented (selectivity) by
contact with a solid phase (catalysts, without change of the solid.
The lattice dynamics of molecular crystals has undergone an enor
mous progress in these last twenty years or so. The experimental
and theoretical advances have been realized by two different
approaches. From one side molecular spectroscopists have been
primarily interested in the vibrational properties of the molecules
themselves subjected to the perturbing influence of the crystal
environment. From the other side the lattice dynamical theory
familiar in solid state physics for atomic lattices has been
extended to molecular arrays. Although the overlap between the two
approaches has been considerable the reference material is rather
scattered in specialized papers. The purpose of this book is to
partly fill this gap and to discuss the lattice dynamical theory of
molecular crystals in a compact and specialized form. As such, the
book is not intended exclusively for researchers and specialists in
the field but also for graduate students entering an activity in
solid state mo lecular spectroscopy."
The aim of these notes is to offer a modern picture of the pertur
bative approach to the calculation of intermolecular forces. The
point of view taken is that a perturbative series truncated at a
low order can provide a valuable way for valuating interaction
energies, especial ly if one limits oneself to the case of
intermediate- and long-range distances between the interacting
partners. Although the situation corresponding to short distances
is essen tially left out from our presentation, the problems which
are within the range of the theory form a vast and important class:
a large var iety of phenomena of matter, in fact, depends on the
existence of in teractions among atoms or molecules, which over a
substantial range of distances should be classified as weak in
comparison to the interactions occurring inside atoms or molecules.
We are aware of the omission of some topics, which in principle
could have been included in our review. For instance, a very scarce
at tention has been paid to the analysis of problems involving
interacting partners in degenerate states, which is of particular
relevance in the case of interactions between excited atoms (only a
rather quick presen tation of the formal apparatus of degenerate
perturbation theory is in cluded in Chap. III). Interactions
involving the simultaneous presence of more than two atoms (or
mOlecules) have not been considered, with the consequent
non-necessity of considering nonadditive effects which characterize
the general N-body problem."
The 14th Jerusalem Symposium continued the tradition of the
pleasant and exciting meetings which once a year gather
distinguished scientists, the world's most renowned experts in
specific fields of quantum chemistry and biochemistry, in the
impressive surroundings of the Israel Academy of Sciences and
Humanities. The subject discussed this year - Intermolecular forces
- is one of the utmost interest for all molecular sciences. I wish
to thank all those who made this meeting possible and contributed
toits success: the Baron Edmond de Rothschild whose continuous
generosity guarantees the perenniality of our venture, t e Israel
Academy of Sciences and in particular its Vice-President, Pr fes
sor Yoshua Jortner for his devoted contribution to the organization
and holding of this meeting, the high authorities of the Hebrew Uni
versity of Jerusalem and in particular the Rector Meshulamfor their
constant support and Dr. Pierre Claverie for his efficient help in
the preparation of the program. Mrs Abigail Hyam and Mrs
MyriamYogev must be thanked for their contribution to the
efficiency and success of the local arrangements. Bernard Pullman
ix B.Pullman ed.}, IntermolecularForces, ix. Copyright
(c)1981byD.ReidelPublishingCompany. INTERMOLECULAR FORCES: WHAT CAN
BE LEARNED FROM AB INITIO CALCULATIONS? Advan der Avoird Institute
of Theoretical Chemistry, University of Nijmegen, Toernooiveld,
Nijmegen, The Netherlands. 1. INTRODUCTION Various experiments, suc
as elastic or rotationally inelastic molecular beamscattering(1,2
and spectroscopic studies of so-cafled Van der Waals
molecules(3,4), have been designed especially to provide
information about the Van der Waals interactions between
molecules."
Analytical chemistry of the recent years is strongly influenced by
automation. Data acquisition from analytica instruments - and some
times also controlling of instruments - by a computer are
principally solved since many years. Availability of microcomputers
made these tasks also feasible from the economic point of view.
Besides these basic applications of computers in chemical
measurements scientists developed computer programs for solving
more sophisticated problems for which some kind of "intelligence"
is usually supposed to be necessary. Harm less numerical
experiments on this topic led to passionate discussions about the
theme "which jobs cannot be done by a computer but only by human
brain ? . If this question is useful at all it should not be ans
wered a priori. Application of computers in chemistry is a matter
of utility, sometimes it is a social problem, but it is never a
question of piety for the human brain. Automated instruments and
the necessity to work on complex pro blems enhanced the development
of automatic methods for the reduction and interpretation of large
data sets. Numerous methods from mathematics, statistics,
information theory, and computer science have been exten sively
investigated for the elucidation of chemical information; a new
discipline "chemometrics" has been established. Three different
approaches have been used for computer-assisted interpretations of
chemical data. 1. Heuristic methods try to formu late computer
programs working in a similar way as a chemist would solve the
problem. 2."
1. 1 STATEMENT OF THE PROBLEM Quantum chemistry judged not from the
ever present possibility of unex pected developments but on the
basis of the achievements in the last fifty years, is predominantly
limited to attempts to solve for the energy and expectation values
of wave functions representing, in the limit, an exact solution to
the Schroedinger equation. Because of well-known dif ficulties in
system with more than about 50 electrons, the adopted ap
proximations are generally rather crude. As examples of quantum
chemical approximations we mention the total or partial neglects of
electron correlation, the neglect of relativistic effects, the use
of subminimal basis sets, the still present neglect of inner-core
electrons in semi-empirical methods, the acceptance of the
Born-Oppenheimer approximations, and so on. In general, the larger
the system, in terms of the number of electrons, the cruder the
approxima tion. In a way, the present status of quantum chemistry
might appear as nearly paradoxical. Indeed, for small systems,
where very accurate ex periments are often available, and
therefore, there is not a great need to obtain (from quantum
chemistry) predictions of new data but rather, a theoretical
interpretation of the existing data, we find increasi gly powerful
and reliable quantum chemical methods and techniques."
Since the discovery of quantum mechanics, more than fifty years
ago, the theory of chemical reactivity has taken the first steps of
its development. The knowledge of the electronic structure and the
properties of atoms and molecules is the basis for an un
derstanding of their interactions in the elementary act of any
chemical process. The increasing information in this field during
the last decades has stimulated the elaboration of the methods for
evaluating the potential energy of the reacting systems as well as
the creation of new methods for calculation of reaction probabili
ties (or cross sections) and rate constants. An exact solution to
these fundamental problems of theoretical chemistry based on quan
tum mechanics and statistical physics, however, is still impossible
even for the simplest chemical reactions. Therefore, different ap
proximations have to be used in order to simplify one or the other
side of the problem. At present, the basic approach in the theory
of chemical reactivity consists in separating the motions of
electrons and nu clei by making use of the Born-Oppenheimer
adiabatic approximation to obtain electronic energy as an effective
potential for nuclear motion. If the potential energy surface is
known, one can calculate, in principle, the reaction probability
for any given initial state of the system. The reaction rate is
then obtained as an average of the reaction probabilities over all
possible initial states of the reacting artic1es. In the different
stages of this calculational scheme additional approximations are
usually introduced."
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