Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

Anne Marie March, Tadesse A. Assefa, Christina Boemer, Christian Bressler, Alexander Britz, Michael Diez, Gilles Doumy, Andreas Galler, Manuel Harder, Dmitry Khakhulin, Zoltán Németh, Mátyás Pápai, Sebastian Schulz, Stephen H. Southworth, Hasan Yavaş, Linda Young, Wojciech Gawelda, G. Vankó

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

We probe the dynamics of valence electrons in photoexcited [Fe(terpy)2]2+ in solution to gain deeper insight into the Fe-ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making it a powerful technique for molecular studies in a wide variety of environments. A picosecond-time-resolved measurement of the complete 1s X-ray emission spectrum captures the transient photoinduced changes and includes the weak valence-to-core (vtc) emission lines that correspond to transitions from occupied valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitals directly involved in the light-driven dynamics; a change in the metal-ligand orbital overlap results in an intensity reduction and a blue energy shift in agreement with our theoretical calculations and more subtle features at the highest energies reflect changes in the frontier orbital populations.

Original languageEnglish
Pages (from-to)2620-2626
Number of pages7
JournalJournal of Physical Chemistry C
Volume121
Issue number5
DOIs
Publication statusPublished - Feb 9 2017

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Ligands
valence
orbitals
Molecular orbitals
Time measurement
spectroscopy
x rays
Metals
X rays
ligands
Electrons
molecular orbitals
emission spectra
penetration
time measurement
X-Ray Emission Spectrometry
energy
probes
sensitivity
shift

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy. / March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina; Bressler, Christian; Britz, Alexander; Diez, Michael; Doumy, Gilles; Galler, Andreas; Harder, Manuel; Khakhulin, Dmitry; Németh, Zoltán; Pápai, Mátyás; Schulz, Sebastian; Southworth, Stephen H.; Yavaş, Hasan; Young, Linda; Gawelda, Wojciech; Vankó, G.

In: Journal of Physical Chemistry C, Vol. 121, No. 5, 09.02.2017, p. 2620-2626.

Research output: Contribution to journalArticle

March, AM, Assefa, TA, Boemer, C, Bressler, C, Britz, A, Diez, M, Doumy, G, Galler, A, Harder, M, Khakhulin, D, Németh, Z, Pápai, M, Schulz, S, Southworth, SH, Yavaş, H, Young, L, Gawelda, W & Vankó, G 2017, 'Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy', Journal of Physical Chemistry C, vol. 121, no. 5, pp. 2620-2626. https://doi.org/10.1021/acs.jpcc.6b12940
March, Anne Marie ; Assefa, Tadesse A. ; Boemer, Christina ; Bressler, Christian ; Britz, Alexander ; Diez, Michael ; Doumy, Gilles ; Galler, Andreas ; Harder, Manuel ; Khakhulin, Dmitry ; Németh, Zoltán ; Pápai, Mátyás ; Schulz, Sebastian ; Southworth, Stephen H. ; Yavaş, Hasan ; Young, Linda ; Gawelda, Wojciech ; Vankó, G. / Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy. In: Journal of Physical Chemistry C. 2017 ; Vol. 121, No. 5. pp. 2620-2626.
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AU - Schulz, Sebastian

AU - Southworth, Stephen H.

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