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

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4];  [2];  [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)
+ Show Author Affiliations
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+.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1503401
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 4 Vol. 123; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (10)

Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy journal October 2019
Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy journal January 2020
Toward Luminescent Iron Complexes: Unravelling the Photophysics by Computing Potential Energy Surfaces journal May 2019
Excited-state solvation structure of transition metal complexes from molecular dynamics simulations and assessment of partial atomic charge methods journal January 2019
The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems journal May 2008
Simulation of ultrafast excited-state dynamics and elastic x-ray scattering by quantum wavepacket dynamics journal September 2019
Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy text January 2020
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering text January 2020
Excited-State Solvation Structure of Transition Metal Complexes from Molecular Dynamics Simulations and Assessment of Partial Atomic Charge Methods text January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY