The Ultrafast Quantum Dynamics of Photoexcited Adenine–Thymine Basepair Investigated with a Fragment-based Diabatization and a Linear Vibronic Coupling Model

2021 ◽  
Vol 125 (40) ◽  
pp. 8912-8924
Author(s):  
Martha Yaghoubi Jouybari ◽  
James A. Green ◽  
Roberto Improta ◽  
Fabrizio Santoro
Keyword(s):  
Quantum Dynamics ◽  
Coupling Model ◽  
Vibronic Coupling ◽  
Adenine Thymine

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>

scholarly journals Parameterization of a linear vibronic coupling model with multiconfigurational electronic structure methods to study the quantum dynamics of photoexcited pyrene

2021 ◽  
Vol 154 (10) ◽  
pp. 104106
Author(s):  
Flavia Aleotti ◽  
Daniel Aranda ◽  
Martha Yaghoubi Jouybari ◽  
Marco Garavelli ◽  
Artur Nenov ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Quantum Dynamics ◽  
Coupling Model ◽  
Vibronic Coupling ◽  
Electronic Structure Methods

An alternative model of the vibronic coupling in octahedral complexes

1988 ◽  
Vol 53 (6) ◽  
pp. 1134-1140
Author(s):  
Martin Breza ◽  
Peter Pelikán
Keyword(s):  
Linear Regression ◽  
Alternative Model ◽  
Potential Surface ◽  
Analytical Formula ◽  
Coupling Model ◽  
Regression Method ◽  
Vibronic Coupling ◽  
Linear Regression Method ◽  
Active Systems ◽  
Jahn Teller

It is suggested that for some transition metal hexahalo complexes, the Eg-(a1g + eg) vibronic coupling model is better suited than the classical T2g-(a1g + eg) model. For the former, alternative model, the potential constants in the analytical formula are evaluated from the numerical map of the adiabatic potential surface by using the linear regression method. The numerical values for 29 hexahalo complexes of the 1st row transition metals are obtained by the CNDO/2 method. Some interesting trends of parameters of such Jahn-Teller-active systems are disclosed.

ChemInform Abstract: A Trimer Vibronic Coupling Model for Triptycene: The Jahn-Teller and Barnett Effects.

ChemInform ◽  
2010 ◽  
Vol 24 (33) ◽  
pp. no-no
Author(s):  
M. J. RILEY ◽  
A. FURLAN ◽  
H. U. GUEDEL ◽  
S. LEUTWYLER
Keyword(s):  
Coupling Model ◽  
Vibronic Coupling ◽  
Jahn Teller

Perturbation solutions of a two state–two mode vibronic coupling model

1980 ◽  
Vol 72 (12) ◽  
pp. 6777-6781 ◽  
Author(s):  
İlker Özkan ◽  
Lionel Goodman
Keyword(s):  
Coupling Model ◽  
Vibronic Coupling ◽  
Perturbation Solutions

scholarly journals A trimer vibronic coupling model for triptycene: The Jahn–Teller and Barnett effects

1993 ◽  
Vol 98 (5) ◽  
pp. 3803-3815 ◽  
Author(s):  
Mark J. Riley ◽  
Alan Furlan ◽  
Hans U. Güdel ◽  
Samuel Leutwyler
Keyword(s):  
Coupling Model ◽  
Vibronic Coupling ◽  
Jahn Teller
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