Published December 21, 2015 | Version v1
Journal article

The consequences of improperly describing oscillator strengths beyond the electric dipole approximation

  • 1. Department of Chemistry, University of Washington, Seattle, Washington 98195 (United States)

Description

The interaction between a quantum mechanical system and plane wave light is usually modeled within the electric dipole approximation. This assumes that the intensity of the incident field is constant over the length of the system and transition probabilities are described in terms of the electric dipole transition moment. For short wavelength spectroscopies, such as X-ray absorption, the electric dipole approximation often breaks down. Higher order multipoles are then included to describe transition probabilities. The square of the magnetic dipole and electric quadrupole are often included, but this results in an origin-dependent expression for the oscillator strength. The oscillator strength can be made origin-independent if all terms through the same order in the wave vector are retained. We will show the consequences and potential pitfalls of using either of these two expressions. It is shown that the origin-dependent expression may violate the Thomas-Reiche-Kuhn sum rule and the origin-independent expression can result in negative transition probabilities

Additional details

Identifiers

Publishing Information

Journal Title
Journal of Chemical Physics
Journal Volume
143
Journal Issue
23
Journal Page Range
p. 234103-234103.8
ISSN
0021-9606
CODEN
JCPSA6

Optional Information

Notes
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