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Title: Beyond the electric-dipole approximation: A formulation and implementation of molecular response theory for the description of absorption of electromagnetic field radiation

We present a formulation of molecular response theory for the description of a quantum mechanical molecular system in the presence of a weak, monochromatic, linearly polarized electromagnetic field without introducing truncated multipolar expansions. The presentation focuses on a description of linear absorption by adopting the energy-loss approach in combination with the complex polarization propagator formulation of response theory. Going beyond the electric-dipole approximation is essential whenever studying electric-dipole-forbidden transitions, and in general, non-dipolar effects become increasingly important when addressing spectroscopies involving higher-energy photons. These two aspects are examined by our study of the near K-edge X-ray absorption fine structure of the alkaline earth metals (Mg, Ca, Sr, Ba, and Ra) as well as the trans-polyenes. In following the series of alkaline earth metals, the sizes of non-dipolar effects are probed with respect to increasing photon energies and a detailed assessment of results is made in terms of studying the pertinent transition electron densities and in particular their spatial extension in comparison with the photon wavelength. Along the series of trans-polyenes, the sizes of non-dipolar effects are probed for X-ray spectroscopies on organic molecules with respect to the spatial extension of the chromophore.
Authors:
;  [1] ; ;  [2] ;  [3]
  1. Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, DK-5230 Odense M (Denmark)
  2. Department of Physics, Chemistry and Biology, Linköping University, Linköping SE 58183 (Sweden)
  3. Laboratoire de Chimie et Physique Quantiques, UMR 5626—CNRS/Université Toulouse III (Paul Sabatier), 118 route de Narbonne, F-31062 Toulouse Cedex (France)
Publication Date:
OSTI Identifier:
22490830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 24; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 97 MATHEMATICAL METHODS AND COMPUTING; ABSORPTION; ALKALINE EARTH METALS; APPROXIMATIONS; COMPARATIVE EVALUATIONS; ELECTRIC DIPOLES; ELECTROMAGNETIC FIELDS; ELECTRON DENSITY; ENERGY LOSSES; FINE STRUCTURE; FORBIDDEN TRANSITIONS; MONOCHROMATIC RADIATION; PHOTONS; POLARIZATION; POLYENES; QUANTUM MECHANICS; WAVELENGTHS; X RADIATION; X-RAY SPECTROSCOPY