Fragment Diabatization Linear Vibronic Coupling Model for Quantum Dynamics of Multichromophoric Systems: Population of the Charge-Transfer State in the Photoexcited Guanine–Cytosine Pair

2021 ◽  
Author(s):  
James A. Green ◽  
Martha Yaghoubi Jouybari ◽  
Haritha Asha ◽  
Fabrizio Santoro ◽  
Roberto Improta
Keyword(s):  
Charge Transfer ◽  
Quantum Dynamics ◽  
Coupling Model ◽  
Vibronic Coupling ◽  
Charge Transfer State ◽  
Transfer State

scholarly journals A Fragment Diabatization Linear Vibronic Coupling Model for Quantum Dynamics of Multichromophoric Systems: Population of the Charge Transfer State in the Photoexcited Guanine Cytosine Pair

2021 ◽  
Author(s):  
James Green ◽  
Martha Yaghoubi Jouybari ◽  
Haritha Asha ◽  
Fabrizio Santoro ◽  
Roberto Improta
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Quantum Dynamics ◽  
Reorganization Energy ◽  
Coupling Model ◽  
Vibronic Coupling ◽  
Strongly Coupled ◽  
Exciton Localization ◽  
Td Dft

<div>We introduce a method (FrD-LVC) based on a fragment diabatization (FrD) for the parametrization of a Linear Vibronic Coupling (LVC) model suitable for studying the photophysics of multichromophore systems. In combination with effective quantum dynamics (QD) propagations with multilayer multiconfigurational time-dependent Hartree (ML-MCTDH), the FrD-LVC approach gives access to the study of the competition between intra-chromophore decays, like those at conical intersections, and inter-chromophore processes, like exciton localization/delocalization and the involvement of charge transfer (CT) states. We used FrD-LVC parametrized with TD-DFT calculations, adopting either CAM-B3LYP or ωB97X-D functionals, to study the ultrafast photoexcited QD of a Guanine-Cytosine (GC) hydrogen bonded pair, within a Watson-Crick arrangement, considering up to 12 coupled diabatic electronic states and the effect of all the 99 vibrational coordinates. The bright excited states localized on C and, especially, on G are predicted to be strongly coupled to the G->C CT state which is efficiently and quickly populated after an excitation to any of the four lowest energy bright local excited states. Our QD simulations show that more than 80% of the excited population on G and ~50% of that on C decays to this CT state in less than 50 fs. We investigate the role of vibronic effects in the population of the CT state and show it depends mainly on its large reorganization energy so that it can occur even when it is significantly less stable than the bright states in the Franck-Condon region. At the same time, we document that the formation of the GC pair almost suppresses the involvement of dark nπ* excited states in the photoactivated dynamics.</div>

scholarly journals A Fragment Diabatization Linear Vibronic Coupling Model for Quantum Dynamics of Multichromophoric Systems: Population of the Charge Transfer State in the Photoexcited Guanine Cytosine Pair

2021 ◽  
Author(s):  
James Green ◽  
Martha Yaghoubi Jouybari ◽  
Haritha Asha ◽  
Fabrizio Santoro ◽  
Roberto Improta
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Quantum Dynamics ◽  
Reorganization Energy ◽  
Coupling Model ◽  
Vibronic Coupling ◽  
Strongly Coupled ◽  
Exciton Localization ◽  
Td Dft

<div>We introduce a method (FrD-LVC) based on a fragment diabatization (FrD) for the parametrization of a Linear Vibronic Coupling (LVC) model suitable for studying the photophysics of multichromophore systems. In combination with effective quantum dynamics (QD) propagations with multilayer multiconfigurational time-dependent Hartree (ML-MCTDH), the FrD-LVC approach gives access to the study of the competition between intra-chromophore decays, like those at conical intersections, and inter-chromophore processes, like exciton localization/delocalization and the involvement of charge transfer (CT) states. We used FrD-LVC parametrized with TD-DFT calculations, adopting either CAM-B3LYP or ωB97X-D functionals, to study the ultrafast photoexcited QD of a Guanine-Cytosine (GC) hydrogen bonded pair, within a Watson-Crick arrangement, considering up to 12 coupled diabatic electronic states and the effect of all the 99 vibrational coordinates. The bright excited states localized on C and, especially, on G are predicted to be strongly coupled to the G->C CT state which is efficiently and quickly populated after an excitation to any of the four lowest energy bright local excited states. Our QD simulations show that more than 80% of the excited population on G and ~50% of that on C decays to this CT state in less than 50 fs. We investigate the role of vibronic effects in the population of the CT state and show it depends mainly on its large reorganization energy so that it can occur even when it is significantly less stable than the bright states in the Franck-Condon region. At the same time, we document that the formation of the GC pair almost suppresses the involvement of dark nπ* excited states in the photoactivated dynamics.</div>

The Jahn–Teller effect in the lowest charge transfer state of UF6

1978 ◽  
Vol 68 (9) ◽  
pp. 4066-4072 ◽  
Author(s):  
E. R. Bernstein ◽  
G. R. Meredith ◽  
J. D. Webb
Keyword(s):  
Charge Transfer ◽  
Teller Effect ◽  
Charge Transfer State ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Transfer State

The charge-transfer state of 4-dimethylamino-3,5-dimethylbenzonitrile studied in a free jet

1987 ◽  
Vol 141 (5) ◽  
pp. 450-454 ◽  
Author(s):  
T. Kobayashi ◽  
M. Futakami ◽  
O. Kajimoto
Keyword(s):  
Charge Transfer ◽  
Charge Transfer State ◽  
Free Jet ◽  
Transfer State

Charge Transfer State Versus Hot Exciton Dissociation in Polymer−Fullerene Blended Solar Cells

2010 ◽  
Vol 132 (34) ◽  
pp. 11878-11880 ◽  
Author(s):  
Jiye Lee ◽  
Koen Vandewal ◽  
Shane R. Yost ◽  
Matthias E. Bahlke ◽  
Ludwig Goris ◽  
...  
Keyword(s):  
Solar Cells ◽  
Charge Transfer ◽  
Charge Transfer State ◽  
Exciton Dissociation ◽  
Transfer State
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