title: The consequences of improperly describing oscillator strengths beyond the electric dipole approximation.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Lestrange
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.
authors.forename: Franco
authors.initials: F
authors.lastname: Egidi
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.
authors.forename: Xiaosong
authors.initials: X
authors.lastname: Li