Journal Article

PUBDB-2018-04105

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)$_5$ , Fe(CO)$_4$ , and Fe(CO)$_3$

Leitner, T.Extern* ; Josefsson, I. ; Mazza, T.XFEL.EU* ; Miedema, P. S.DESY* ; Schröder, H. ; Beye, M.DESY* ; Kunnus, K. ; Schreck, S. ; Düsterer, S.DESY* ; Föhlisch, A.Extern* ; Meyer, M.XFEL.EU* ; Odelius, M. ; Wernet, P. (Corresponding author)Extern*

2018
American Institute of Physics Melville, NY

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Please use a persistent id in citations: doi:10.1063/1.5035149  doi:10.3204/PUBDB-2018-04105

Abstract: The prototypical photoinduced dissociation of Fe(CO)$_5$ in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO)$_5$ successively dissociates to Fe(CO)$_4$ and Fe(CO)$_3$ along a pathway where both fragments retain the singlet multiplicity of Fe(CO)$_5$. The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO)$_4$ and Fe(CO)$_3$ with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valence-orbital interactions upon Fe–CO dissociation, thereby validating fundamental theoretical concepts in Fe–CO bonding. Chemical shifts of CO 3$σ$ inner-valence and Fe 3p core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. It could also serve as a benchmark for how charge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy.

Note: Published by AIP Publishing.

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Contributing Institute(s):

1. FLASH Photonen-Diagnose und Steuerungen (FS-FLASH-D)
2. DOOR-User (DOOR)
3. FS-FLASH (FS-FLASH)

Research Program(s):

1. 6213 - Materials and Processes for Energy and Transport Technologies (POF3-621) (POF3-621)
2. 6G2 - FLASH (POF3-622) (POF3-622)

Experiment(s):

1. FLASH Beamline PG2 (FLASH)

Appears in the scientific report 2018

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; IF < 5 ; JCR ; NCBI Molecular Biology Database ; National-Konsortium ; Nationallizenz ; PubMed Central ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Web of Science Core Collection

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