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. 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. 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 referenced in this record:
A new record excited state 3 MLCT lifetime for metalorganic iron( ii ) complexes
journal, January 2016
- Liu, Li; Duchanois, Thibaut; Etienne, Thibaud
- Physical Chemistry Chemical Physics, Vol. 18, Issue 18
Ab Initio Nonadiabatic Quantum Molecular Dynamics
journal, February 2018
- Curchod, Basile F. E.; Martínez, Todd J.
- Chemical Reviews, Vol. 118, Issue 7
ONIOM approach for non-adiabatic on-the-fly molecular dynamics demonstrated for the backbone controlled Dewar valence isomerization
journal, May 2012
- Fingerhut, Benjamin P.; Oesterling, Sven; Haiser, Karin
- The Journal of Chemical Physics, Vol. 136, Issue 20
Reparameterization of hybrid functionals based on energy differences of states of different multiplicity
journal, December 2001
- Reiher, Markus; Salomon, Oliver; Artur Hess, Bernd
- Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 107, Issue 1
Trajectory Surface-Hopping Dynamics Including Intersystem Crossing in [Ru(bpy) 3 ] 2+
journal, August 2017
- Atkins, Andrew J.; González, Leticia
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 16
Iron sensitizer converts light to electrons with 92% yield
journal, October 2015
- Harlang, Tobias C. B.; Liu, Yizhu; Gordivska, Olga
- Nature Chemistry, Vol. 7, Issue 11
Tracking the picosecond deactivation dynamics of a photoexcited iron carbene complex by time-resolved X-ray scattering
journal, January 2018
- Leshchev, Denis; Harlang, Tobias C. B.; Fredin, Lisa A.
- Chemical Science, Vol. 9, Issue 2
Solution Structure and Ultrafast Vibrational Relaxation of the PtPOP Complex Revealed by ΔSCF-QM/MM Direct Dynamics Simulations
journal, February 2018
- Levi, Gianluca; Pápai, Mátyás; Henriksen, Niels E.
- The Journal of Physical Chemistry C, Vol. 122, Issue 13
Photophysics of a copper phenanthroline elucidated by trajectory and wavepacket-based quantum dynamics: a synergetic approach
journal, January 2017
- Capano, G.; Penfold, T. J.; Chergui, M.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 30
Chemistry with ADF
journal, January 2001
- te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
- Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993
- Klamt, A.; Schüürmann, G.
- J. Chem. Soc., Perkin Trans. 2, Issue 5
The Nose–Hoover thermostat
journal, October 1985
- Evans, D. J.; Holian, B. L.
- The Journal of Chemical Physics, Vol. 83, Issue 8
A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution
journal, August 2006
- Improta, Roberto; Barone, Vincenzo; Scalmani, Giovanni
- The Journal of Chemical Physics, Vol. 125, Issue 5
Conservation of vibrational coherence in ultrafast electronic relaxation: The case of diplatinum complexes in solution
journal, September 2017
- Monni, Roberto; Auböck, Gerald; Kinschel, Dominik
- Chemical Physics Letters, Vol. 683
Comparison of Different Three-site Interaction Potentials for Liquid Acetonitrile
journal, April 2001
- Guàrdia, E.; Pinzón, R.; Casulleras, J.
- Molecular Simulation, Vol. 26, Issue 4
Effect of tert -Butyl Functionalization on the Photoexcited Decay of a Fe(II)- N -Heterocyclic Carbene Complex
journal, July 2016
- Pápai, Mátyás; Penfold, Thomas J.; Møller, Klaus B.
- The Journal of Physical Chemistry C, Vol. 120, Issue 31
Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2′-bipyridine)(CN) 4 ] 2−
journal, January 2018
- Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.
- Physical Chemistry Chemical Physics, Vol. 20, Issue 6
The multiconfiguration time-dependent Hartree (MCTDH) method: a highly efficient algorithm for propagating wavepackets
journal, January 2000
- Beck, M.
- Physics Reports, Vol. 324, Issue 1
Ultrafast Photophysics of Transition Metal Complexes
journal, February 2015
- Chergui, Majed
- Accounts of Chemical Research, Vol. 48, Issue 3
Atomistic characterization of the active-site solvation dynamics of a model photocatalyst
journal, November 2016
- van Driel, Tim B.; Kjær, Kasper S.; Hartsock, Robert W.
- Nature Communications, Vol. 7, Issue 1
Towards longer-lived metal-to-ligand charge transfer states of iron(ii) complexes: an N-heterocyclic carbene approach
journal, January 2013
- Liu, Yizhu; Harlang, Tobias; Canton, Sophie E.
- Chemical Communications, Vol. 49, Issue 57
Nonadiabatic molecular dynamics with solvent effects: A LR-TDDFT QM/MM study of ruthenium (II) tris (bipyridine) in water
journal, November 2011
- Tavernelli, Ivano; Curchod, Basile F. E.; Rothlisberger, Ursula
- Chemical Physics, Vol. 391, Issue 1
Solvent Effects on Electronically Excited States: QM/Continuum Versus QM/Explicit Models
journal, February 2018
- De Vetta, Martina; Menger, Maximilian F. S. J.; Nogueira, Juan J.
- The Journal of Physical Chemistry B, Vol. 122, Issue 11
Mixed Quantum/Classical Method for Nonadiabatic Quantum Dynamics in Explicit Solvent Models: The ππ */nπ* Decay of Thymine in Water as a Test Case
journal, January 2018
- Cerezo, Javier; Liu, Yanli; Lin, Na
- Journal of Chemical Theory and Computation, Vol. 14, Issue 2
Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis
journal, April 1990
- Breneman, Curt M.; Wiberg, Kenneth B.
- Journal of Computational Chemistry, Vol. 11, Issue 3
Fe N -Heterocyclic Carbene Complexes as Promising Photosensitizers
journal, July 2016
- Liu, Yizhu; Persson, Petter; Sundström, Villy
- Accounts of Chemical Research, Vol. 49, Issue 8
Light-induced spin crossover in Fe(II)-based complexes: The full photocycle unraveled by ultrafast optical and X-ray spectroscopies
journal, November 2010
- Cannizzo, A.; Milne, C. J.; Consani, C.
- Coordination Chemistry Reviews, Vol. 254, Issue 21-22
Reading and writing single-atom magnets
journal, March 2017
- Natterer, Fabian D.; Yang, Kai; Paul, William
- Nature, Vol. 543, Issue 7644
The multi-configurational time-dependent Hartree approach
journal, January 1990
- Meyer, H. -D.; Manthe, U.; Cederbaum, L. S.
- Chemical Physics Letters, Vol. 165, Issue 1
Ultrafast Nonadiabatic Dynamics of [Fe II (bpy) 3 ] 2+ in Solution
journal, July 2007
- Gawelda, Wojciech; Cannizzo, Andrea; Pham, Van-Thai
- Journal of the American Chemical Society, Vol. 129, Issue 26
Molecular and Interfacial Calculations of Iron(II) Light Harvesters
journal, March 2016
- Fredin, Lisa A.; Wärnmark, Kenneth; Sundström, Villy
- ChemSusChem, Vol. 9, Issue 7
High-Efficiency Iron Photosensitizer Explained with Quantum Wavepacket Dynamics
journal, May 2016
- Pápai, Mátyás; Vankó, György; Rozgonyi, Tamás
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 11
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
Hydrogen from photo-catalytic water splitting process: A review
journal, March 2015
- Ahmad, H.; Kamarudin, S. K.; Minggu, L. J.
- Renewable and Sustainable Energy Reviews, Vol. 43
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996
- Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian
- Journal of the American Chemical Society, Vol. 118, Issue 45
Ultrafast Excited-State Dynamics of Copper(I) Complexes
journal, February 2015
- Iwamura, Munetaka; Takeuchi, Satoshi; Tahara, Tahei
- Accounts of Chemical Research, Vol. 48, Issue 3
The ultrafast X-ray spectroscopic revolution in chemical dynamics
journal, May 2018
- Kraus, Peter M.; Zürch, Michael; Cushing, Scott K.
- Nature Reviews Chemistry, Vol. 2, Issue 6
Multimode vibronic coupling effects in molecules
journal, March 1981
- Cederbaum, L. S.; Köppel, H.; Domcke, W.
- International Journal of Quantum Chemistry, Vol. 20, Issue S15
A Multiple-Time-Step Molecular Dynamics Algorithm for Macromolecules
journal, July 1994
- Humphreys, Darryl D.; Friesner, Richard A.; Berne, Bruce J.
- The Journal of Physical Chemistry, Vol. 98, Issue 27
Molecular dynamics with coupling to an external bath
journal, October 1984
- Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
- The Journal of Chemical Physics, Vol. 81, Issue 8
A Quantum Dynamics Study of the Ultrafast Relaxation in a Prototypical Cu(I)–Phenanthroline
journal, October 2014
- Capano, G.; Chergui, M.; Rothlisberger, U.
- The Journal of Physical Chemistry A, Vol. 118, Issue 42
Computational Photophysics in the Presence of an Environment
journal, April 2018
- Nogueira, Juan J.; González, Leticia
- Annual Review of Physical Chemistry, Vol. 69, Issue 1
Spin-Vibronic Quantum Dynamics for Ultrafast Excited-State Processes
journal, February 2015
- Eng, Julien; Gourlaouen, Christophe; Gindensperger, Etienne
- Accounts of Chemical Research, Vol. 48, Issue 3
A simplified relativistic time-dependent density-functional theory formalism for the calculations of excitation energies including spin-orbit coupling effect
journal, October 2005
- Wang, Fan; Ziegler, Tom
- The Journal of Chemical Physics, Vol. 123, Issue 15
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
journal, March 1998
- Barone, Vincenzo; Cossi, Maurizio
- The Journal of Physical Chemistry A, Vol. 102, Issue 11
Nonadiabatic Molecular Dynamics Simulations: Synergies between Theory and Experiments
journal, February 2015
- Tavernelli, Ivano
- Accounts of Chemical Research, Vol. 48, Issue 3
Nonequilibrium solvation: An ab initio quantum‐mechanical method in the continuum cavity model approximation
journal, May 1993
- Aguilar, M. A.; Olivares del Valle, F. J.; Tomasi, J.
- The Journal of Chemical Physics, Vol. 98, Issue 9
Ligand substitution and conformational effects on the ultrafast luminescent decay of [Re(CO) 3 (phen)(L)] + (L = imidazole, pyridine): non-adiabatic quantum dynamics
journal, January 2018
- Fumanal, M.; Gindensperger, E.; Daniel, C.
- Physical Chemistry Chemical Physics, Vol. 20, Issue 2
Ultrafast Deactivation Mechanism of the Excited Singlet in the Light-Induced Spin Crossover of [Fe(2,2′-bipyridine) 3 ] 2+
journal, November 2013
- Sousa, Carmen; de Graaf, Coen; Rudavskyi, Andrii
- Chemistry - A European Journal, Vol. 19, Issue 51
Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution
journal, June 2018
- Monni, Roberto; Capano, Gloria; Auböck, Gerald
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 28
Spin-Vibronic Mechanism for Intersystem Crossing
journal, March 2018
- Penfold, Thomas J.; Gindensperger, Etienne; Daniel, Chantal
- Chemical Reviews, Vol. 118, Issue 15
Photocatalytic Water Splitting: Recent Progress and Future Challenges
journal, September 2010
- Maeda, Kazuhiko; Domen, Kazunari
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 18, p. 2655-2661
Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics
journal, April 2018
- Crespo-Otero, Rachel; Barbatti, Mario
- Chemical Reviews, Vol. 118, Issue 15
Theoretical Investigation of the Electronic Structure of Fe(II) Complexes at Spin-State Transitions
journal, December 2012
- Pápai, Mátyás; Vankó, György; de Graaf, Coen
- Journal of Chemical Theory and Computation, Vol. 9, Issue 1
Ultrafast Excited-State Decays in [Re(CO) 3 (N,N)(L)] n + : Nonadiabatic Quantum Dynamics
journal, February 2017
- Fumanal, Maria; Gindensperger, Etienne; Daniel, Chantal
- Journal of Chemical Theory and Computation, Vol. 13, Issue 3
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr
journal, April 1994
- Schäfer, Ansgar; Huber, Christian; Ahlrichs, Reinhart
- The Journal of Chemical Physics, Vol. 100, Issue 8
An Iron-Based Photosensitizer with Extended Excited-State Lifetime: Photophysical and Photovoltaic Properties: An Iron-Based Photosensitizer with Extended Excited-State Lifetime
journal, April 2015
- Duchanois, Thibaut; Etienne, Thibaud; Cebrián, Cristina
- European Journal of Inorganic Chemistry, Vol. 2015, Issue 14
Relativistic regular two‐component Hamiltonians
journal, September 1993
- Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
- The Journal of Chemical Physics, Vol. 99, Issue 6
Recent Progress in Ultrafast X-ray Diffraction
journal, April 2006
- Bargheer, M.; Zhavoronkov, N.; Woerner, M.
- ChemPhysChem, Vol. 7, Issue 4
Assessment of Density Functionals for the High-Spin/Low-Spin Energy Difference in the Low-Spin Iron(II) Tris(2,2′-bipyridine) Complex
journal, July 2005
- Lawson Daku, Latévi Max; Vargas, Alfredo; Hauser, Andreas
- ChemPhysChem, Vol. 6, Issue 7
Spin-Transition Polymers: From Molecular Materials Toward Memory Devices
journal, January 1998
- Kahn, O.
- Science, Vol. 279, Issue 5347
Photochemical Conversion of Solar Energy
journal, February 2008
- Balzani, Vincenzo; Credi, Alberto; Venturi, Margherita
- ChemSusChem, Vol. 1, Issue 1-2
Time-dependent density functional theory for molecules in liquid solutions
journal, September 2001
- Cossi, Maurizio; Barone, Vincenzo
- The Journal of Chemical Physics, Vol. 115, Issue 10
Vibrational Relaxation and Intersystem Crossing of Binuclear Metal Complexes in Solution
journal, January 2011
- van der Veen, Renske M.; Cannizzo, Andrea; van Mourik, Frank
- Journal of the American Chemical Society, Vol. 133, Issue 2
Ultrafast Electron Diffraction (UED): A New Development for the 4D Determination of Transient Molecular Structures
journal, June 2003
- Srinivasan, Ramesh; Lobastov, Vladimir A.; Ruan, Chong-Yu
- Helvetica Chimica Acta, Vol. 86, Issue 6
Semiclassical simulation of photochemical reactions in condensed phase
journal, February 2003
- Persico, Maurizio; Granucci, Giovanni; Inglese, Silvia
- Journal of Molecular Structure: THEOCHEM, Vol. 621, Issue 1-2
Molecular dynamics---Scalable algorithms for molecular dynamics simulations on commodity clusters
conference, January 2006
- Bowers, Kevin J.; Sacerdoti, Federico D.; Salmon, John K.
- Proceedings of the 2006 ACM/IEEE conference on Supercomputing - SC '06
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
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
- Malmqvist, Per Åke; Pierloot, Kristine; Shahi, Abdul Rehaman Moughal
- The Journal of Chemical Physics, Vol. 128, Issue 20
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
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
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
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
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
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering
text, January 2020
- Kunnus, Kristjan; Vacher, Morgane; Harlang, Tobias C. B.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy
text, January 2020
- Tatsuno, Hideyuki; Kjær, Kasper S.; Kunnus, Kristjan
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Excited-State Solvation Structure of Transition Metal Complexes from Molecular Dynamics Simulations and Assessment of Partial Atomic Charge Methods
text, January 2018
- Abedi, Mostafa; Levi, Gianluca; Zederkof, Diana B.
- arXiv