Change search
ReferencesLink to record
Permanent link

Direct link
Beyond the electric-dipole approximation: A formulation and implementation of molecular response theory for the description of absorption of electromagnetic field radiation
University of Southern Denmark, Denmark.
Linköping University, Department of Physics, Chemistry and Biology, Theoretical Chemistry. Linköping University, Faculty of Science & Engineering.
University of Toulouse 3, France.
University of Southern Denmark, Denmark.
Show others and affiliations
2015 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 142, no 24, 244111- p.Article 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.

Place, publisher, year, edition, pages
American Institute of Physics (AIP) , 2015. Vol. 142, no 24, 244111- p.
National Category
Chemical Sciences
URN: urn:nbn:se:liu:diva-120463DOI: 10.1063/1.4922697ISI: 000357615100015PubMedID: 26133414OAI: diva2:845563

Funding Agencies|Lundbeck Foundation; Danish Council for Independent Research; Knut and Alice Wallenberg Foundation [KAW-2013.0020]; Swedish Research Council [621-2014-4646]

Available from: 2015-08-12 Created: 2015-08-11 Last updated: 2015-08-13

Open Access in DiVA

fulltext(1787 kB)158 downloads
File information
File name FULLTEXT01.pdfFile size 1787 kBChecksum SHA-512
Type fulltextMimetype application/pdf

Other links

Publisher's full textPubMed

Search in DiVA

By author/editor
Kauczor, JoannaNorman, Patrick
By organisation
Theoretical ChemistryFaculty of Science & Engineering
In the same journal
Journal of Chemical Physics
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar
Total: 158 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 328 hits
ReferencesLink to record
Permanent link

Direct link