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Title: Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH

Abstract

Here, we utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)5 in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)4 which are observed following a charge transfer photoexcitation of Fe(CO)5 as reported in our previous study. We find that branching of the reaction pathway likely happens in the 1A1 state of Fe(CO)4. A sub-picosecond time constant of the spin crossover from 1B2 to 3B2 is rationalized by the proposed 1B21A13B2 mechanism. Ultrafast ligation of the 1B2 Fe(CO)4 state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the 3B2 Fe(CO)4 ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via 1B21A11A' Fe(CO)4EtOH pathway and the time scale of the 1A1 Fe(CO)4 state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.

Authors:
 [1];  [2];  [3];  [1];  [4];  [4];  [4];  [3];  [3];  [5];  [6];  [6];  [6];  [7];  [7];  [4];  [8];  [9];  [10];  [2] more »;  [4];  [1] « less
  1. Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy; Univ. Potsdam, Potsdam (Germany). Institut fur Physik und Astronomie
  2. Stockholm Univ. (Sweden). Department of Physics
  3. Max Planck Institute for Biophysical Chemistry, Am Fassberg, Gottingen (Germany)
  4. Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States). PULSE Institute
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
  8. MAX-lab, Lund (Sweden)
  9. Utrecht Univ. Utrecht (Netherlands). Department of Chemistry
  10. Max Planck Institute for Biophysical Chemistry, Am Fassberg, Gottingen (Germany); Gottingen Univ. (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1242357
Alternate Identifier(s):
OSTI ID: 1335953
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Structural Dynamics
Additional Journal Information:
Journal Volume: 3; Journal Issue: 4; Journal ID: ISSN 2329-7778
Publisher:
American Crystallographic Association/AIP
Country of Publication:
United States
Language:
English
Subject:
43 PARTICLE ACCELERATORS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kunnus, K., Josefsson, I., Rajkovic, I., Schreck, S., Quevedo, W., Beye, M., Weniger, C., Grübel, S., Scholz, M., Nordlund, D., Zhang, W., Hartsock, R. W., Gaffney, K. J., Schlotter, W. F., Turner, J. J., Kennedy, B., Hennies, F., de Groot, F. M. F., Techert, S., Odelius, M., Wernet, Ph., and Föhlisch, A. Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH. United States: N. p., 2016. Web. doi:10.1063/1.4941602.
Kunnus, K., Josefsson, I., Rajkovic, I., Schreck, S., Quevedo, W., Beye, M., Weniger, C., Grübel, S., Scholz, M., Nordlund, D., Zhang, W., Hartsock, R. W., Gaffney, K. J., Schlotter, W. F., Turner, J. J., Kennedy, B., Hennies, F., de Groot, F. M. F., Techert, S., Odelius, M., Wernet, Ph., & Föhlisch, A. Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH. United States. https://doi.org/10.1063/1.4941602
Kunnus, K., Josefsson, I., Rajkovic, I., Schreck, S., Quevedo, W., Beye, M., Weniger, C., Grübel, S., Scholz, M., Nordlund, D., Zhang, W., Hartsock, R. W., Gaffney, K. J., Schlotter, W. F., Turner, J. J., Kennedy, B., Hennies, F., de Groot, F. M. F., Techert, S., Odelius, M., Wernet, Ph., and Föhlisch, A. 2016. "Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH". United States. https://doi.org/10.1063/1.4941602. https://www.osti.gov/servlets/purl/1242357.
@article{osti_1242357,
title = {Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH},
author = {Kunnus, K. and Josefsson, I. and Rajkovic, I. and Schreck, S. and Quevedo, W. and Beye, M. and Weniger, C. and Grübel, S. and Scholz, M. and Nordlund, D. and Zhang, W. and Hartsock, R. W. and Gaffney, K. J. and Schlotter, W. F. and Turner, J. J. and Kennedy, B. and Hennies, F. and de Groot, F. M. F. and Techert, S. and Odelius, M. and Wernet, Ph. and Föhlisch, A.},
abstractNote = {Here, we utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)5 in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)4 which are observed following a charge transfer photoexcitation of Fe(CO)5 as reported in our previous study. We find that branching of the reaction pathway likely happens in the 1A1 state of Fe(CO)4. A sub-picosecond time constant of the spin crossover from 1B2 to 3B2 is rationalized by the proposed 1B2 → 1A1 → 3B2 mechanism. Ultrafast ligation of the 1B2 Fe(CO)4 state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the 3B2 Fe(CO)4 ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via 1B2 → 1A1 → 1A' Fe(CO)4EtOH pathway and the time scale of the 1A1 Fe(CO)4 state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.},
doi = {10.1063/1.4941602},
url = {https://www.osti.gov/biblio/1242357}, journal = {Structural Dynamics},
issn = {2329-7778},
number = 4,
volume = 3,
place = {United States},
year = {Tue Feb 09 00:00:00 EST 2016},
month = {Tue Feb 09 00:00:00 EST 2016}
}

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Ultrafast Photophysics of Transition Metal Complexes
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Reaction kinetics of coordinatively unsaturated iron carbonyls formed on gas-phase excimer laser photolysis of iron pentacarbonyl
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Optical spectra of transition-metal carbonyls: chromium hexacarbonyl, iron pentacarbonyl, and nickel tetracarbonyl
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Pentacarbonyliron(0) photocatalyzed hydrogenation and isomerization of olefins
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Dynamics of Photosubstitution Reactions of Fe(CO) 5 :  An Ultrafast Infrared Study of High Spin Reactivity
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Ultrafast Nonadiabatic Dynamics of [Fe II (bpy) 3 ] 2+ in Solution
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journal, March 2011


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journal, June 2012


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Dispersion at Millimeter Wavelengths in Methyl and Ethyl Alcohols
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Molecular motions in liquid. I. Rotation of water and small alcohols studied by deuteron relaxation
journal, October 1976


Fragmentation and molecular dynamics in the laser photodissociation of iron pentacarbonyl
journal, January 1981


The ultrafast photodissociation of Fe(CO)5 in the gas phase
journal, April 1998


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journal, September 2014


The liquid-liquid phase transition in silicon revealed by snapshots of valence electrons
journal, August 2010


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journal, January 2009


Real-Time Observation of Surface Bond Breaking with an X-ray Laser
journal, March 2013


Probing the transition state region in catalytic CO oxidation on Ru
journal, February 2015


The Nature of Simple Photodissociation Reactions in Liquids on Ultrafast Time Scales
journal, October 1988


Connecting Chemical Dynamics in Gases and Liquids
journal, May 2006


The soft x-ray instrument for materials studies at the linac coherent light source x-ray free-electron laser
text, January 2012


Agostic interactions in transition metal compounds
text, January 2007


Orbital-specific mapping of the ligand exchange dynamics of $Fe(CO)_{5}$ in solution
text, January 2015


Works referencing / citing this record:

Time-resolved X-ray spectroscopies of chemical systems: New perspectives
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Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)5 via a singlet pathway upon excitation at 266 nm
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Perspective: Opportunities for ultrafast science at SwissFEL
journal, November 2017


Modeling core-level excitations with variationally optimized reduced-density matrices and the extended random phase approximation
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Comparison of multireference ab initio wavefunction methodologies for X-ray absorption edges: A case study on [Fe(II/III)Cl 4 ] 2–/1– molecules
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Theoretical X‐ray spectroscopy of transition metal compounds
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Roadmap of ultrafast x-ray atomic and molecular physics
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Preface to the Special Edition on Femtochemistry and “The Hamburg Conference on Femtochemistry 2015 (FEMTO12)”
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Perspective: Opportunities for ultrafast science at SwissFEL
text, January 2017


Roadmap of ultrafast x-ray atomic and molecular physics
journal, January 2018


Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)$_5$ via a singlet pathway upon excitation at 266 nm
text, January 2017


Perspective: Opportunities for ultrafast science at SwissFEL
text, January 2017


Short-wavelength free-electron laser sources and science: a review
journal, October 2017


Roadmap of ultrafast x-ray atomic and molecular physics
text, January 2018


Time-resolved X-ray spectroscopies of chemical systems: New perspectives
journal, May 2016


Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers
journal, April 2019


Preface to the Special Edition on Femtochemistry and “The Hamburg Conference on Femtochemistry 2015 (FEMTO12)”
text, January 2016


Perspective: Opportunities for ultrafast science at SwissFEL
text, January 2017