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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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Distributed Polarizabilities

Distributed Polarizabilities

(p.159) 9 Distributed Polarizabilities
The Theory of Intermolecular Forces

Anthony J. Stone

Oxford University Press

Just as the charge distribution of a molecule is better described by multipoles distributed around the molecule rather than all at one point, so the polarizability of a molecule is better described by distributed rather than central polarizabilities. The treatment is more complicated, however, because polarization of one atom in a molecule changes its local multipole moments and induces additional electric fields that polarize other atoms. Ways to handle this problem are discussed, including ways of defining local polarizabilities that incorporate the secondary polarization effects. This approach also leads to a justification of the local atom—atom dispersion model that is almost universally used for large molecules.

Keywords:   Applequist model, Thole damping, distributed polarizabilities, local polarizabilities, distributed dispersion

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