I N l E - R N A T I O N A I . J O U R N A I . OF O U A N T U M CHEMISTRY. VOL 47.
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Book Review
Density-Functional Theory of Atoms and Molecules. R.G. Parr and W. Yang, Oxford
University Press, New York, Oxford, 1989. IX + 333 pp. Price f45.00.
Density-functional theory is probably most well known for its tremendous success in the
theory of extended systems. Thanks particularly to the so-called local density approximation, it
has been possible to create a really fruitful interaction between experimentalists and theoreticians
working in a broad area of solid-state problems.
The book by Parr and Yang focuses on partially different aspects of density-functional
theory. As the title of their book indicates, they emphasize applications to systems with a
finite number of electrons. That is perhaps more a presentation of a program than a review of
actual applications, which have, after all, been relatively scarce so far. One of the objectives
of the present book is, however, to show that quantum chemists-not to say chemists in
general-have a lot to gain obtaining insight into the structure of density-functional theory.
The first two chapters are devoted to a quick review of some fundamental aspects of “tra-
ditional” quantum theory, which form the natural connection to density-functional theory. The
key concepts are the variational principle, Hartree-Fock, correlation, the Hellmann-Feynman
theorem, and density matrices. With a Hamiltonian containing one- and two-electron operators,
one can express expectation values in terms of first- and second-order reduced density matrices.
Since the density-the key concept in density-functional theories-can be obtained from the
more general quantity density matrix, one of the surprising aspects of density-functional theory
is that, according to the Hohenberg-Kohn theorem, the total energy can also be written as a
functional of the density.
The analogy between density-functional theory for ground states, on the one hand, and
thermodynamics as a theory of equilibrium states, on the other, plays an important role in the
book by Parr and Yang. The “philosophy” and the fundamentals of density-functional theory
is introduced in Chapter 3, which ends with three sections on finite temperature theory. The
following chapters presents a very careful discussion of the chemical potential and its role in
density-functional theory. In Chapter 5, various kinds of derivatives of the chemical potential are
related to chemical concepts like electronegativity, hardness and softness, and reactivity indices.
The Kohn-Sham method, which might be called a practical implementation of abstract
density-functional theory, is treated in three chapters in which the intricacies of these procedures
are very carefully analyzed. Chapter 10 is a review of some applications to atoms and small
molecules.
The book ends with a chapter on some special topics and with seven very useful appendices.
The first of these is a summary of the theory of functionals, which will probably by very
welcome for many chemists who may have some vague idea of what is meant by a functional
but do not really feel sure how to handle it. The last appendix is a review-not just a list-of
the review literature on density-functional theory. There is also an extensive bibliography t b +
includes the titles of the papers.
The book by Parr and Yang constitutes a very valuable addition to the growing literature
on density-functional theory, primarily since it introduces topics that are often absent in other
presentations. But it is also written in a style that makes the reading pleasant and interesting.
JEAN-LOUIS
CALAIS
0 1993 John Wiley & Sons, Inc. CCC 0020-7608/93/010101-01
