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Title: Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer

Abstract

The solvent-mediated excited-state dynamics of the COOH-functionalized Fe-carbene photosensitizer [Fe(bmicp)2]2+ (bmicp = 2,6-bis(3-methyl-imidazole-1-ylidine)-4-carboxy-pyridine) is studied by time-dependent density functional theory, as well as classical and quantum dynamics simulations. We demonstrate the crucial role of the polar acetonitrile solvent in stabilizing the metal-to-ligand charge transfer (MLCT) states of the investigated molecule using the conductor polarizable continuum model. This leads to dynamics that avoid sub-ps back electron transfer to the metal and an exceptionally long-lived 1MLCT state that does not undergo sub-ps 1MLCT → 3MLCT intersystem crossing as it is energetically isolated. We identify two components of the excited-state solvent reorganization process: an initial rotation (~300 fs) and diffusional dynamics within the local cage surrounding the rotated solvent molecule (~2 ps). Lastly, it is found that the relaxation of the solvent only slightly affects the excited-state population dynamics of [Fe(bmicp)2]2+.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [2]; ORCiD logo [2]
  1. Technical Univ. of Denmark, Lyngby (Denmark); Hungarian Academy of Sciences, Budapest (Hungary)
  2. Technical Univ. of Denmark, Lyngby (Denmark)
  3. Technical Univ. of Denmark, Lyngby (Denmark); Univ. of Ireland, Reykjavik (Ireland)
  4. Technical Univ. of Denmark, Lyngby (Denmark); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1503401
Grant/Contract Number:  
AC02-76SF00515; 609405; LP2013-59; 4002-00272; 8021-00347B
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 4; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pápai, Mátyás, Abedi, Mostafa, Levi, Gianluca, Biasin, Elisa, Nielsen, Martin M., and Møller, Klaus B. Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.8b10768.
Pápai, Mátyás, Abedi, Mostafa, Levi, Gianluca, Biasin, Elisa, Nielsen, Martin M., & Møller, Klaus B. Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer. United States. doi:https://doi.org/10.1021/acs.jpcc.8b10768
Pápai, Mátyás, Abedi, Mostafa, Levi, Gianluca, Biasin, Elisa, Nielsen, Martin M., and Møller, Klaus B. Thu . "Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer". United States. doi:https://doi.org/10.1021/acs.jpcc.8b10768. https://www.osti.gov/servlets/purl/1503401.
@article{osti_1503401,
title = {Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer},
author = {Pápai, Mátyás and Abedi, Mostafa and Levi, Gianluca and Biasin, Elisa and Nielsen, Martin M. and Møller, Klaus B.},
abstractNote = {The solvent-mediated excited-state dynamics of the COOH-functionalized Fe-carbene photosensitizer [Fe(bmicp)2]2+ (bmicp = 2,6-bis(3-methyl-imidazole-1-ylidine)-4-carboxy-pyridine) is studied by time-dependent density functional theory, as well as classical and quantum dynamics simulations. We demonstrate the crucial role of the polar acetonitrile solvent in stabilizing the metal-to-ligand charge transfer (MLCT) states of the investigated molecule using the conductor polarizable continuum model. This leads to dynamics that avoid sub-ps back electron transfer to the metal and an exceptionally long-lived 1MLCT state that does not undergo sub-ps 1MLCT → 3MLCT intersystem crossing as it is energetically isolated. We identify two components of the excited-state solvent reorganization process: an initial rotation (~300 fs) and diffusional dynamics within the local cage surrounding the rotated solvent molecule (~2 ps). Lastly, it is found that the relaxation of the solvent only slightly affects the excited-state population dynamics of [Fe(bmicp)2]2+.},
doi = {10.1021/acs.jpcc.8b10768},
journal = {Journal of Physical Chemistry. C},
number = 4,
volume = 123,
place = {United States},
year = {2019},
month = {1}
}

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Works referencing / citing this record:

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy
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  • Kunnus, Kristjan; Vacher, Morgane; Harlang, Tobias C. B.
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Excited-state solvation structure of transition metal complexes from molecular dynamics simulations and assessment of partial atomic charge methods
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  • Abedi, Mostafa; Levi, Gianluca; Zederkof, Diana B.
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 7
  • DOI: 10.1039/c8cp06567e

Simulation of ultrafast excited-state dynamics and elastic x-ray scattering by quantum wavepacket dynamics
journal, September 2019

  • Pápai, Mátyás; Rozgonyi, Tamás; Penfold, Thomas J.
  • The Journal of Chemical Physics, Vol. 151, Issue 10
  • DOI: 10.1063/1.5115204