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Beyond the electric-dipole approximation: A formulation and implementation of molecular response theory for the description of absorption of electromagnetic field radiation
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2015 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 142, no 24, 244111Article in journal (Refereed) Published
Abstract [en]

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. © 2015 AIP Publishing LLC.

Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2015. Vol. 142, no 24, 244111
Keyword [en]
Alkaline earth metals, Barium, Chromophores, Electromagnetic fields, Energy dissipation, Organic compounds, Photons, Polarization, Quantum theory, X ray absorption, X ray spectroscopy, Assessment of results, Complex polarization propagator, Electric-dipole approximation, Electromagnetic field radiation, Forbidden transitions, Higher energy photons, Multipolar expansion, X ray absorption fine structures, Electromagnetic field theory, alkaline earth metal, magnesium, polyene, chemical structure, chemistry, conformation, electromagnetic field, photon, radiation absorption, theoretical model, Absorption, Radiation, Metals, Alkaline Earth, Models, Molecular, Models, Theoretical, Molecular Conformation, Polyenes
National Category
Theoretical Chemistry
URN: urn:nbn:se:kth:diva-198712DOI: 10.1063/1.4922697ISI: 000357615100015ScopusID: 2-s2.0-84933574277OAI: diva2:1059127

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