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American Institute of Physics, Structural Dynamics, 6(3), p. 062601

DOI: 10.1063/1.4961953

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Towards an ab initio theory for metal L-edge soft X-ray spectroscopy of molecular aggregates

Journal article published in 2016 by Marie Preuße, Sergey I. Bokarev ORCID, Saadullah G. Aziz, Oliver Kühn
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

The Frenkel exciton model was adapted to describe X-ray absorption and resonant inelastic scattering spectra of polynuclear transition metal complexes by means of the restricted active space self-consistent field method. The proposed approach allows to substantially decrease the requirements on computational resources if compared to a full supermolecular quantum chemical treatment. This holds true, in particular, in cases where the dipole approximation to the electronic transition charge density can be applied. The computational protocol was applied to the calculation of X-ray spectra of the hemin complex, which forms dimers in aqueous solution. The aggregation effects were found to be comparable to the spectral alterations due to the replacement of the axial ligand by solvent molecules.