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Cook 1974

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9 views

Cook 1974

Uploaded by

chengawy7
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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1 INTRODUCTION

It is a striking paradox that quantum chemists, who in many


universities and research institutes are the major users of
computing facilities, are seeking essentially qualitative
results. Their gigantic computer investigations into
molecular electronic structure are largely the use of
quantitative methods to obtain insight into the qualitative
concepts used by experimental chemists. Of course, any
investigation of qualitative ideas of "bonding", "valence" etc.
is made much more precise and convincing by the successful
prediction of molecular properties or the computation of
electron densities which agree with diffraction data.
However, the quantum chemist's plan is "to find out what
electrons are doing in molecules" and the computation of
molecular parameters is, in the main, a source of evidence
rather than an end in itself.

In the strict terminology of quantum theory many of the


chemists concepts are not "observables"; there is no hope of
isolating a double bond, a localised molecular orbital, a bond
polarity or even a bond energy. Nevertheless, much of
chemistry and biochemistry is expressed in terms of these
concepts and they have their own historical and methodological
justification in practice - in any case they ante^date quantum
theory and can be used autonomously. In order to maintain
contact with and to influence the main stream of chemical
1
Introduction

thinking quantum chemistry must apply itself to the analysis,


criticism and quantitative investigation of these concepts
within the rigorous discipline of quantum theory. The
construction of well-defined theoretical models which embody
the ideas and experience of chemists enables a thoroughgoing
examination of the strengths and weaknesses of the underlying
assumptions to be made.
In addition to this "interpretative" function quantitative
valence calculations have an important and decisive role to play
when it is beyond the wit or technique of experimental workers
to obtain certain critical data. The theories of chemistry
often interpret observable phenomena in terms of the interaction
of unobservable "effects" and frequently a phenomenon is a
balance of two or more of these effects acting in opposition.
In such a case almost any observation can be explained in
terms of the relative strengths of the opposing effects and
the whole explanation sounds rather hollow. It is in
precisely these situations where the quantitative nature of
computational methods can make a decisive contribution. A
computation of the magnitudes of the various factors involved
is much more convincing than the use of indirectly inferred
quantities. Investigations of this kind enable the concepts
and effects with a valid theoretical and physical background
to be sorted from effects which are simply names.

In practice the efforts of the experimentalist and the


computational worker are complementary. It is impossible for
the experimental chemist to find out what forces are involved
when (say) a protein molecule has its conformation forcibly
changed; at a particular site in one amino acid constituent.
Contrariwise, the computational worker would quickly be
swamped by numerical problems in any serious attempt to
investigate (say) the effect of variations in ionic strength
on the configuration of a protein. The experimental worker
is, for the theoretician, a constant source of challenging
problems and the quantum chemist can suggest fruitful lines
of research to the experimentalist.
2
Introduction

The various branches of spectroscopy present problems of


a quite different character; here it is necessary to have a
detailed knowledge of the energy-level structure of molecules,
radicals and ions. The use of quantum mechanical calculations
to interpret the interaction of radiation with matter over a
large range of energy presents computational quantum chemistry
with its severest quantitative test. There is a wealth of
detailed experimental knowledge about the excited states of
molecular systems ranging from X-ray transitions to NMR
nuclear couplings. Attempts have been made to use molecular
wave-functions to compute the transition energies of all of
these spectra with differing degrees of success. The main
result is a sound qualitative understanding of the dependence
of the transition energies on molecular parameters.
Finally the most ambitious, and to chemists the most
valuable, project: the computation of reaction paths. The
difficulties here are ones of scale; the computation of the
total energy of a composite system of two or more fragments in
a large number of configurations. The only feasible study
which can be made by the methods outlined in the following
chapters is that of gas phase reactions between simple
molecules which constitutes a very small part of chemistry.
Solvents and catalysts play such an important role in the vast
bulk of chemistry and biochemistry that, at the present time,
the only contribution to this field we can sensibly make is
to wish experimental workers luck in developing empirical
theories.
No attempt is made in the rest of this work to pursue
particular applications: the methods of quantum chemical
calculations are developed.

SUGGESTIONS FOR FURTHER READING


"Nature of Quantum Chemistry" P.-O. Löwdin in Int.J.Quant.Chem.,
l_, 7 (1967)

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