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:
-
- Technical Univ. of Denmark, Lyngby (Denmark); Hungarian Academy of Sciences, Budapest (Hungary)
- Technical Univ. of Denmark, Lyngby (Denmark)
- Technical Univ. of Denmark, Lyngby (Denmark); Univ. of Ireland, Reykjavik (Ireland)
- 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}
}
Web of Science
Works referencing / citing this record:
Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy
journal, October 2019
- Tatsuno, Hideyuki; Kjær, Kasper S.; Kunnus, Kristjan
- Angewandte Chemie, Vol. 132, Issue 1
Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy
journal, January 2020
- Tatsuno, Hideyuki; Kjær, Kasper S.; Kunnus, Kristjan
- Angewandte Chemie International Edition, Vol. 59, Issue 1
Toward Luminescent Iron Complexes: Unravelling the Photophysics by Computing Potential Energy Surfaces
journal, May 2019
- Francés‐Monerris, Antonio; Gros, Philippe C.; Assfeld, Xavier
- ChemPhotoChem, Vol. 3, Issue 9
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering
journal, January 2020
- Kunnus, Kristjan; Vacher, Morgane; Harlang, Tobias C. B.
- Nature Communications, Vol. 11, Issue 1
Excited-state solvation structure of transition metal complexes from molecular dynamics simulations and assessment of partial atomic charge methods
journal, January 2019
- Abedi, Mostafa; Levi, Gianluca; Zederkof, Diana B.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 7
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