Endre søk
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf
From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni2+ in Aqueous Solutions with Resonant Inelastic X-ray Scattering
Stockholms universitet, Naturvetenskapliga fakulteten, Fysikum.ORCID-id: 0000-0002-8621-4282
Vise andre og tillknytning
Rekke forfattare: 102013 (engelsk)Inngår i: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 117, s. 16512-16521Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Bonding of the Ni2+(aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d–3d electron correlation interactions in the Ni2+(aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d–3d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV–vis spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra.

sted, utgiver, år, opplag, sider
2013. Vol. 117, s. 16512-16521
HSV kategori
Forskningsprogram
fysik
Identifikatorer
URN: urn:nbn:se:su:diva-119836DOI: 10.1021/jp4100813ISI: 000329331800016OAI: oai:DiVA.org:su-119836DiVA, id: diva2:848759
Tilgjengelig fra: 2015-08-26 Laget: 2015-08-26 Sist oppdatert: 2019-12-17bibliografisk kontrollert
Inngår i avhandling
1. Structure and dynamics in solution – the core electron perspective
Åpne denne publikasjonen i ny fane eller vindu >>Structure and dynamics in solution – the core electron perspective
2015 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

This thesis is based on theoretical studies of the molecular and electronic structure of solvated ions and molecules. Very detailed information of the system can be obtained from theoretical calculations, but a realistic model is dependent on an accurate computational method. Accurate calculations of core level electronic spectra, and evaluation of the modeling against experiments, are central parts of this work. The main tools used for characterization of the systems are high-level quantum chemistry and molecular dynamics simulations. 

Molecular components in solutions are involved in many key processes converting sunlight into chemical or electrical energy. Transition metal complexes, with their pronounced absorption in the visible light region of the electromagnetic spectrum, are core components in various energy conversion applications, and the iodide/triiodide redox couple is a commonly used electrolyte. The local structure of the electronic valence in transition metal complexes and the details of the solvation mechanisms of electrolyte solutions are investigated through the combination of computational modeling and core level spectroscopy. The studies of model systems show that interactions between the solute and solvent are important for the electronic structure, and knowledge of the details in model systems studied can be relevant for energy conversion applications. Furthermore, high-level quantum chemistry has been applied for interpreting time-resolved spectra, where the electronic structure of a metal complex is followed during a photoinduced chemical reaction in solution.

With advanced modeling in combination with recent experimental developments, more complex problems than previously addressed can be dissected.

sted, utgiver, år, opplag, sider
Stockholm: Department of Physics, Stockholm University, 2015. s. 64
Emneord
quantum chemistry, RASSCF, molecular dynamics, x-ray spectroscopy, electrolyte solutions
HSV kategori
Forskningsprogram
fysik
Identifikatorer
urn:nbn:se:su:diva-119838 (URN)978-91-7649-258-1 (ISBN)
Disputas
2015-10-15, sal FB42, AlbaNova universitetscentrum, Roslagstullsbacken 21, Stockholm, 10:00 (engelsk)
Opponent
Veileder
Merknad

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 8: Manuscript.

Tilgjengelig fra: 2015-09-23 Laget: 2015-08-26 Sist oppdatert: 2019-10-07bibliografisk kontrollert

Open Access i DiVA

Fulltekst mangler i DiVA

Andre lenker

Forlagets fulltekst

Søk i DiVA

Av forfatter/redaktør
Josefsson, IdaOdelius, Michael
Av organisasjonen
I samme tidsskrift
Journal of Physical Chemistry B

Søk utenfor DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric

doi
urn-nbn
Totalt: 31 treff
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf