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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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Molecules in Electric Fields

Molecules in Electric Fields

(p.13) 2 Molecules in Electric Fields
The Theory of Intermolecular Forces

Anthony J. Stone

Oxford University Press

The idea of multipole moments—charge, dipole, quadrupole, and so on—is developed. The multipole moments are defined and described, first in Cartesian tensor form and then in spherical tensor form. The charge density operator is introduced and its relation to the multipole moments is explained. The energy of a molecule in an external electric field is expressed using multipole moments. Discussion of the response of a molecule to an external electric field, static or oscillating, leads to the concept of polarizabilities and hyperpolarizabilities. The symmetry properties of multipole moments and polarizabilities are examined: if a molecule has any symmetry, some of their components are zero. Changing the origin of coordinates may affect the numerical values of these properties, and formulae are derived for describing the changes.

Keywords:   multipole moments, dipole, quadrupole, cartesian and spherical tensors. polarizabilities, hyperpolarizabilities, frequency-dependent density susceptibility, symmetry properties, change of origin

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