title: Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species.
abstract: X-ray spectroscopies, when combined in laser-pump, X-ray-probe measurement schemes, can be powerful tools for tracking the electronic and geometric structural changes that occur during the course of a photoinitiated chemical reaction. X-ray absorption spectroscopy (XAS) is considered an established technique for such measurements, and X-ray emission spectroscopy (XES) of the strongest core-to-core emission lines (Kα and Kβ) is now being utilized. Flux demanding valence-to-core XES promises to be an important addition to the time-resolved spectroscopic toolkit. In this paper we present measurements and density functional theory calculations on laser-excited, solution-phase ferrocyanide that demonstrate the feasibility of valence-to-core XES for time-resolved experiments. We discuss technical improvements that will make valence-to-core XES a practical pump-probe technique.
authors.affiliation: X-ray Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Anne Marie
authors.initials: AM
authors.lastname: March
authors.affiliation: European XFEL , Albert-Einstein-Ring 19, 22761 Hamburg, Germany.
authors.forename: Tadesse A
authors.initials: TA
authors.lastname: Assefa
authors.affiliation: European XFEL , Albert-Einstein-Ring 19, 22761 Hamburg, Germany ; The Hamburg Centre for Ultrafast Imaging , Luruper Chaussee 149, 22761 Hamburg, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Bressler
authors.affiliation: X-ray Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Gilles
authors.initials: G
authors.lastname: Doumy
authors.affiliation: European XFEL , Albert-Einstein-Ring 19, 22761 Hamburg, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Galler
authors.affiliation: European XFEL , Albert-Einstein-Ring 19, 22761 Hamburg, Germany.
authors.forename: Wojciech
authors.initials: W
authors.lastname: Gawelda
authors.affiliation: X-ray Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Elliot P
authors.initials: EP
authors.lastname: Kanter
authors.affiliation: Wigner Research Centre for Physics, Hungarian Academy Sciences , H-1525 Budapest, Hungary.
authors.forename: Zoltán
authors.initials: Z
authors.lastname: Németh
authors.affiliation: Wigner Research Centre for Physics, Hungarian Academy Sciences , H-1525 Budapest, Hungary.
authors.forename: Mátyás
authors.initials: M
authors.lastname: Pápai
authors.affiliation: X-ray Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Stephen H
authors.initials: SH
authors.lastname: Southworth
authors.affiliation: X-ray Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Linda
authors.initials: L
authors.lastname: Young
authors.affiliation: Wigner Research Centre for Physics, Hungarian Academy Sciences , H-1525 Budapest, Hungary.
authors.forename: György
authors.initials: G
authors.lastname: Vankó