Resonant photoemission at the iron M-edge of Fe(CO)5

Sistrunk, Emily; Grilj, Jakob; McFarland, B. K.; Rohlén, J.; Aguilar, A.; Gühr, Markus

doi:10.1063/1.4827093

Cited by 5 publications

(4 citation statements)

References 35 publications

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“…Based on seminal photoelectron spectroscopy and investigations of Cr(CO) 6 and of CO deposited on surfaces, [79][80][81][82] the broad peak around 36 eV can be straightforwardly assigned to electron emission from the inner-valence 3σ orbital of CO bound in Fe(CO) 5 where the 3σ orbital is derived from the atomic 2s orbitals of C and O. The peak at 63 eV was determined before to arise from the emission from the Fe 3p core level in Fe(CO) 5 , 83 and we FIG. 6.…”

Section: Resultsmentioning

confidence: 98%

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Leitner

Josefsson

Mazza

et al. 2018

The Journal of Chemical Physics

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The prototypical photoinduced dissociation of Fe(CO) 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) successively dissociates to Fe(CO) and Fe(CO) along a pathway where both fragments retain the singlet multiplicity of Fe(CO). The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO) and Fe(CO) 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 3σ 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.

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Section: Resultsmentioning

confidence: 98%

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Leitner

Josefsson

Mazza

et al. 2018

The Journal of Chemical Physics

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“…Furthermore, core-excited state decay in Fe(CO) 5 and Fe(Cp) 2 is dominated by Auger decay, leading to ionic fragments. This is evident from the investigations of Tamenori et al, who reported ion-yield XAS at the Fe M-edge of Fe(CO) 5 and Fe(Cp) 2 and of Heck et al and Sistrunk et al for ion-yield Fe M-edge XAS of Fe(CO) 5 . − By resolving the nature of the various ionic fragments emitted upon X-ray irradiation, so-called partial-ion-yield spectra can be extracted. They contain information on orbital- or state-specific fragmentation of the probed sample. ,,− …”

Section: Introductionmentioning

confidence: 96%

Iron L-Edge Absorption Spectroscopy of Iron Pentacarbonyl and Ferrocene in the Gas Phase

Godehusen

Richter²,

Zimmermann

et al. 2017

J. Phys. Chem. A

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Fe L-edge X-ray absorption spectra of gas-phase iron pentacarbonyl and ferrocene measured in total-ion yield mode are reported. Comparison to previously published spectra of free iron atoms and gaseous iron chloride demonstrates how the interplay of local atomic multiplet effects and orbital interactions in the metal-ligand bonds varies for the different systems. We find changes in the degree of metal-ligand covalency to be reflected in the measured 2p absorption onset. Orbital- or state-specific fragmentation is furthermore investigated in iron pentacarbonyl and ferrocene by analyzing the partial-ion-yield spectra at the Fe L-edge. Strong dependence of the yields of different fragments is observed in ferrocene in contrast to iron pentacarbonyl. This difference is attributed to the different degrees to which the 2p core hole is screened in the two systems and to which charge is rearranged in the Auger final states. We provide experimental benchmark spectra for new ab initio approaches for calculating metal L-edge absorption spectra of metal complexes.

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“…Figure 4 presents the XUV absorption spectrum of groundstate 5 near the Fe M-edge, compared to and characterized by A cubic polynomial fit to the baseline was subtracted from the experimental spectrum to account for contribution from a centrifugal barrier. 87,88 This subtraction is imperfect, resulting in a residual near 52 eV, which is not due to resonant core-to-valence transitions. The raw measured static absorption spectrum and baseline subtraction procedure are outlined in Section S2.1.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Figure 4. Absorption spectrum of ground-state 5.A cubic polynomial fit to the baseline was subtracted from the experimental spectrum to account for contribution from a centrifugal barrier 87,88. This subtraction is imperfect, resulting in a residual near 52 eV, which is not due to resonant core-to-valence transitions.…”

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confidence: 99%

Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO)₅

Troß,

Arias-Martinez,

Carter-Fenk

et al. 2024

J. Am. Chem. Soc.

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Excitation of iron pentacarbonyl [Fe(CO) 5 ], a prototypical photocatalyst, at 266 nm causes the sequential loss of two CO ligands in the gas phase, creating catalytically active, unsaturated iron carbonyls. Despite numerous studies, major aspects of its ultrafast photochemistry remain unresolved because the early excited-state dynamics have so far eluded spectroscopic observation. This has led to the long-held assumption that ultrafast dissociation of gas-phase Fe(CO) 5 proceeds exclusively on the singlet manifold. Herein, we present a combined experimental−theoretical study employing ultrafast extreme ultraviolet transient absorption spectroscopy near the Fe M 2,3 -edge, which features spectral evolution on 100 fs and 3 ps time scales, alongside high-level electronic structure theory, which enables characterization of the molecular geometries and electronic states involved in the ultrafast photodissociation of Fe(CO) 5 . We assign the 100 fs evolution to spectroscopic signatures associated with intertwined structural and electronic dynamics on the singlet metal-centered states during the first CO loss and the 3 ps evolution to the competing dissociation of Fe(CO) 4 along the lowest singlet and triplet surfaces to form Fe(CO) 3 . Calculations of transient spectra in both singlet and triplet states as well as spin−orbit coupling constants along key structural pathways provide evidence for intersystem crossing to the triplet ground state of Fe(CO) 4 . Thus, our work presents the first spectroscopic detection of transient excited states during ultrafast photodissociation of gas-phase Fe(CO) 5 and challenges the longstanding assumption that triplet states do not play a role in the ultrafast dynamics.

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Resonant photoemission at the iron M-edge of Fe(CO)5

Cited by 5 publications

References 35 publications

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Iron L-Edge Absorption Spectroscopy of Iron Pentacarbonyl and Ferrocene in the Gas Phase

Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO)₅

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Resonant photoemission at the iron M-edge of Fe(CO)5

Cited by 5 publications

References 35 publications

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Iron L-Edge Absorption Spectroscopy of Iron Pentacarbonyl and Ferrocene in the Gas Phase

Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO)5

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Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO)₅