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The Theory of Intermolecular Forces$
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Anthony Stone

Print publication date: 2013

Print ISBN-13: 9780199672394

Published to Oxford Scholarship Online: May 2013

DOI: 10.1093/acprof:oso/9780199672394.001.0001

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Perturbation Theory of Intermolecular Forces at Long Range

Perturbation Theory of Intermolecular Forces at Long Range

(p.57) 4 Perturbation Theory of Intermolecular Forces at Long Range
The Theory of Intermolecular Forces

Anthony J. Stone

Oxford University Press

The perturbation theory of intermolecular interactions is in general complicated, but it simplifies considerably if the molecules are sufficiently far apart that the overlap between their electron distributions can be neglected. The theory in this case dates back to London in 1930, but is given here in a more modern form. At first order, the only contribution is the electrostatic interaction discussed in Chaper 3. At second order, there are terms of two kinds. The first is induction, in which each molecule's electron distribution is modified in response to the electrostatic field arising from its neighbours or from external influences. The other is dispersion, in which the natural fluctuations of electron density in each molecule are correlated with those of its neighbours in such a way as to lower the energy. In the development of expressions for these effects It is possible but not necessary to use the multipole expansion.

Keywords:   long-range approximation, polarization approximation, induction, dispersion, polarizability at imaginary frequency, combining rules

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