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 Imre Pápai, Sebastian Schulz, Stephen H. Southworth, Hasan Yavas, Linda Young, Wojciech Gawelda, György Vankó

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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 Is 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
JournalJournal of Physical Chemistry C
Volume121
Issue number5
Pages (from-to)2620-2626
ISSN1932-7447
DOIs
Publication statusPublished - 2017

Cite this

March, A. M., Assefa, T. A., Boemer, C., Bressler, C., Britz, A., Diez, M., ... Vankó, G. (2017). Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy. Journal of Physical Chemistry C, 121(5), 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 Imre ; Schulz, Sebastian ; Southworth, Stephen H. ; Yavas, Hasan ; Young, Linda ; Gawelda, Wojciech ; Vankó, György. / 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.
@article{144b2beafd8f46039879b594615b920a,
title = "Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy",
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 Is 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.",
author = "March, {Anne Marie} and Assefa, {Tadesse A.} and Christina Boemer and Christian Bressler and Alexander Britz and Michael Diez and Gilles Doumy and Andreas Galler and Manuel Harder and Dmitry Khakhulin and Zolt{\'a}n N{\'e}meth and P{\'a}pai, {M{\'a}ty{\'a}s Imre} and Sebastian Schulz and Southworth, {Stephen H.} and Hasan Yavas and Linda Young and Wojciech Gawelda and Gy{\"o}rgy Vank{\'o}",
year = "2017",
doi = "10.1021/acs.jpcc.6b12940",
language = "English",
volume = "121",
pages = "2620--2626",
journal = "The Journal of Physical Chemistry Part C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "5",

}

March, AM, Assefa, TA, Boemer, C, Bressler, C, Britz, A, Diez, M, Doumy, G, Galler, A, Harder, M, Khakhulin, D, Németh, Z, Pápai, MI, Schulz, S, Southworth, SH, Yavas, 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

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 Imre; Schulz, Sebastian; Southworth, Stephen H.; Yavas, Hasan; Young, Linda; Gawelda, Wojciech; Vankó, György.

In: Journal of Physical Chemistry C, Vol. 121, No. 5, 2017, p. 2620-2626.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

AU - March, Anne Marie

AU - Assefa, Tadesse A.

AU - Boemer, Christina

AU - Bressler, Christian

AU - Britz, Alexander

AU - Diez, Michael

AU - Doumy, Gilles

AU - Galler, Andreas

AU - Harder, Manuel

AU - Khakhulin, Dmitry

AU - Németh, Zoltán

AU - Pápai, Mátyás Imre

AU - Schulz, Sebastian

AU - Southworth, Stephen H.

AU - Yavas, Hasan

AU - Young, Linda

AU - Gawelda, Wojciech

AU - Vankó, György

PY - 2017

Y1 - 2017

N2 - 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 Is 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.

AB - 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 Is 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.

U2 - 10.1021/acs.jpcc.6b12940

DO - 10.1021/acs.jpcc.6b12940

M3 - Journal article

VL - 121

SP - 2620

EP - 2626

JO - The Journal of Physical Chemistry Part C

JF - The Journal of Physical Chemistry Part C

SN - 1932-7447

IS - 5

ER -