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Ab initio simulations of core level spectra: Towards an atomistic understanding of the dye-sensitized solar cell
Stockholm University, Faculty of Science, Department of Physics.
2013 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

The main focus of this thesis is ab initio modeling of core level spectra with a high-level quantum chemical description both of the chemical interactions and of local atomic multiplet effects. In particular, the combination of calculations and synchrotron-based core-level spectroscopy aims at understanding the local structure of the electronic valence in transition metal complexes, and the details of the solvation mechanisms of electrolyte solutions, systems relevant for the dye-sensitized solar cell. Configurational sampling in solution is included through molecular dynamics simulations.

Transition metal complexes are studied with x-ray absorption (XA) and resonant inelastic scattering (RIXS) spectroscopy, characterizing excited states with atomic site specificity. The theoretical multiconfigurational method, applying an active-space partitioning of the molecular orbitals (RASSCF), is used to assign the transitions observed in spectra of hydrated Ni2+ explicitly, including charge transfer and multiplet effects.

Furthermore, the solvent-induced binding energy properties of the I- and I3- anions in aqueous, ethanol, and acetonitrile solutions are analyzed using photoelectron spectroscopy (XPS). The study shows that specific ion–solvent interactions are important for the core-level binding energy shifts in solution. The special case with I3- dissolved in water, where hydrogen bonding causes breaking of the molecular symmetry, is treated and proves that the geometry changes influence the photoelectron spectrum of aqueous I3- directly.

Place, publisher, year, edition, pages
Stockholm: Department of Physics, Stockholm University , 2013. , 31 p.
Keyword [en]
multiconfigurational quantum chemistry, CASSCF calculations, core-level spectroscopy, x-ray photoelectron spectroscopy, x-ray absorption, resonant x-ray scattering, dye solar cells, transition metals
National Category
Physical Sciences
Research subject
Chemical Physics
URN: urn:nbn:se:su:diva-93098OAI: diva2:644796
2013-09-23, FA31, Roslagstullsbacken 21, Stockholm, 10:00 (English)
Available from: 2013-09-10 Created: 2013-09-02 Last updated: 2013-10-08Bibliographically approved
List of papers
1. Ab Initio Calculations of X-ray Spectra: Atomic Multiplet and Molecular Orbital Effects in a Multiconfigurational SCF Approach to the L-Edge Spectra of Transition Metal Complexes
Open this publication in new window or tab >>Ab Initio Calculations of X-ray Spectra: Atomic Multiplet and Molecular Orbital Effects in a Multiconfigurational SCF Approach to the L-Edge Spectra of Transition Metal Complexes
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2012 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 3, no 23, 3565-3570 p.Article in journal (Refereed) Published
Abstract [en]

A new ab initio approach to the calculation of X-ray spectra is demonstrated. It combines a high-level quantum chemical description of the chemical interactions and local atomic multiplet effects. We show here calculated L-edge X-ray absorption (XA) and resonant inelastic X-ray scattering spectra for aqueous Ni2+ and XA spectra for a polypyridyl iron complex. Our quantum chemical calculations on a high level of accuracy in a post-Hartree–Fock framework give excellent agreement with experiment. This opens the door to reliable and detailed information on chemical interactions and the valence electronic structure in 3d transition-metal complexes also in transient excited electronic states. As we combine a molecular-orbital description with a proper treatment of local atomic electron correlation effects, our calculations uniquely allow, in particular, identifying the influence of interatomic chemical interactions versus intra-atomic correlations in the L-edge X-ray spectra.

X-ray spectroscopy, spectrum simulations, resonant inelastic X-ray scattering, RASSCF calculations, transition metal ions
National Category
Physical Sciences
Research subject
urn:nbn:se:su:diva-85227 (URN)10.1021/jz301479j (DOI)000312170600029 ()
Swedish Research Council
Available from: 2013-01-07 Created: 2013-01-07 Last updated: 2015-08-26Bibliographically approved

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