Theoretical Investigation of The X-Ray Stark Effect in Small Molecules

Abstract

We have studied the Stark effect in the soft x-ray region for various small molecules by calculating the field-dependent x-ray absorption spectra. This effect is explained in terms of the response of molecular orbitals (core and valence), the molecular dipole moment, and the molecular geometry to the applied electric field. A number of consistent trends are observed linking the computed shifts in absorption energies and intensities with specific features of the molecular electronic structure. We find that both the virtual molecular orbitals (valence and/or Rydberg) as well as the core orbitals contribute to observed trends in a complementary fashion. This initial study highlights the potential impact of x-ray Stark spectroscopy as a tool to study electronic structure and environmental perturbations at a sub-molecular scale.

33 pages, 9 figures, 7 tables, supporting information files available

References in corpus (4)

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• Accurate core excitation and ionization energies from a state-specific coupled-cluster singles and doubles approach
• Transition-Potential Coupled Cluster
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