Molecular-Level Exploration of the Structure-Function Relations Underlying Interfacial Charge Transfer in the Subphthalocyanine/
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 Organic Photovoltaic System

Tinnin, Jacob; Bhandari, Srijana; Zhang, Pengzhi; Aksu, Hüseyin; Maiti, Biswajit; Geva, Eitan; Dunietz, Barry D.; Sun, Xiang; Cheung, Margaret S.

doi:10.1103/physrevapplied.13.054075

Cited by 14 publications

(28 citation statements)

References 58 publications

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“…The fact that both the timescale and kinetics of the ππ *→CT1 transition are strongly conformation-dependent can be viewed as a structure–function relation, where the molecular structure (triad conformation) is seen to have a rather dramatic effect on the function (the CT rate). Thus, the triad provides a relatively simple demonstration for the potential importance of such structure–function relations in more complex systems, such as the correlation between interfacial structure and interfacial CT rates in OPV materials. ,, …”

Section: Resultsmentioning

confidence: 99%

“…The LSC NE-FGR and IMT open the door to the investigation of nonequilibrium effects on CT and energy transfer rates in many systems of current technological and biological interest, including confined molecular systems, condensed-phase systems, and semiconductor interfaces . Work on such extensions is underway and will be reported in future publications.…”

Section: Discussionmentioning

confidence: 99%

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Photoinduced Charge Transfer Dynamics in the Carotenoid–Porphyrin–C₆₀ Triad via the Linearized Semiclassical Nonequilibrium Fermi’s Golden Rule

Tong

Cheung

et al. 2020

J. Phys. Chem. B

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The nonequilibrium Fermi's golden rule (NE-FGR) describes the time-dependent rate coefficient for electronic transitions, when the nuclear degrees of freedom start out in a nonequilibrium state. In this paper, the linearized semiclassical (LSC) approximation of the NE-FGR is used to calculate the photoinduced charge transfer (CT) rates in the carotenoidporphyrin-C 60 molecular triad dissolved in explicit tetrahydrofuran. The initial nonequilibrium state corresponds to impulsive photoexcitation from the equilibrated ground-state to the ππ * state, and the porphyrin-to-C 60 and the carotenoid-to-C 60 CT rates are calculated. Our results show that accounting for the nonequilibrium nature of the initial state significantly enhances the transition rate of the porphyrin-to-C 60 CT process. We also derive an instantaneous Marcus theory (IMT) from LSC NE-FGR, which casts the CT rate coefficients in terms of a Marcuslike expression, with explicitly time-dependent reorganization energy and reaction free energy. IMT is found to reproduce the CT rates in the system under consideration remarkably well.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Photoinduced Charge Transfer Dynamics in the Carotenoid–Porphyrin–C₆₀ Triad via the Linearized Semiclassical Nonequilibrium Fermi’s Golden Rule

Tong

Cheung

et al. 2020

J. Phys. Chem. B

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“…The ability to calculate charge-transfer (CT) rate constants in a complex molecular condensed-phase system accurately and reliably is key for quantitative modeling of many systems with biological and technological importance. − One reason why modeling CT in such complex systems is challenging is the need to combine multiple methodologies, each of which calls for making choices based on the trade-off between accuracy and computational feasibility . This includes the choice of an electronic structure method, the method used for assigning partial charges, and force fields (e.g., polarizable vs. nonpolarizable) …”

Section: Introductionmentioning

confidence: 99%

On the Interplay between Electronic Structure and Polarizable Force Fields When Calculating Solution-Phase Charge-Transfer Rates

Han

Zhang

Aksu

et al. 2020

J. Chem. Theory Comput.

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We present a comprehensive analysis of the interplay between the choice of an electronic structure method and the effect of using polarizable force fields vs. nonpolarizable force fields when calculating solution-phase charge-transfer (CT) rates. The analysis is based on an integrative approach that combines inputs from electronic structure calculations and molecular dynamics simulations and is performed in the context of the carotenoid–porphyrin–C60 molecular triad dissolved in an explicit tetrahydrofuran (THF) liquid solvent. Marcus theory rate constants are calculated for the multiple CT processes that occur in this system based on either polarizable or nonpolarizable force fields, parameterized using density functional theory (DFT) with either the B3LYP or the Baer–Neuhauser–Livshits (BNL) density functionals. We find that the effect of switching from nonpolarizable to polarizable force fields on the CT rates is strongly dependent on the choice of the density functional. More specifically, the rate constants obtained using polarizable and nonpolarizable force fields differ significantly when B3LYP is used, while much smaller changes are observed when BNL is used. It is shown that this behavior can be traced back to the tendency of B3LYP to overstabilize CT states, thereby pushing the underlying electronic transitions to the deep inverted region, where even small changes in the force fields can lead to significant changes in the CT rate constants. Our results demonstrate the importance of combining polarizable force fields with an electronic structure method that can accurately capture the energies of excited CT states when calculating charge-transfer rates.

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“…Recently, we proposed a systematic way to account for the motion of the environment by performing the all-atom MD simulations for the entire system with an explicit environment after ab initio calculation of MD-sampled structures. , The CT rate constant was derived from the linearized semiclassical Fermi’s golden rule (LSC FGR), whose Marcus level of approximation is given by where Γ is the electronic coupling between the donor (initial) and acceptor (final) electronic states, ℏ is the reduced Planck’s constant, ⟨ U ⟩ and σ U 2 are the ensemble average and corresponding variance of the donor–acceptor energy gap U ( R ) = V D ( R ) – V A ( R ), respectively. Here, V D/A ( R ) is the donor- or acceptor-state potential energy surface and R is the nuclear configuration of the entire system.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Charge-Transfer Landscape Manifesting the Structure–Rate Relationship in the Condensed Phase Via Machine Learning

Brian

Sun

2021

J. Phys. Chem. B

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In this work, we develop a machine learning (ML) strategy to map the molecular structure to condensed phase charge-transfer (CT) properties including CT rate constants, energy levels, electronic couplings, energy gaps, reorganization energies, and reaction free energies which are called CT fingerprints. The CT fingerprints of selected landmark structures covering the conformation space of an organic photovoltaic molecule dissolved in an explicit solvent are computed and used to train ML models using kernel ridge regression. The ML models show high predictive power with R 2 > 0.97 and both mean absolute error and root-mean-square error within chemical accuracy. The CT landscape for millions of molecular dynamics sampled structures is thus constructed, which allows for instant prediction of CT rate properties, given any conformation of the molecule. We demonstrate some immediate utilities of the CT landscape such as calculating the ensemble-averaged CT rate constant and interpreting the effects of molecular structural features on the CT rate. The unprecedented CT landscape will be useful for investigating real-time CT dynamics in nanoscale-and mesoscale-condensed phase systems and for the optimal fabrication design for homogeneous and heterogeneous optoelectronic devices.

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Molecular-Level Exploration of the Structure-Function Relations Underlying Interfacial Charge Transfer in the Subphthalocyanine/ C60 Organic Photovoltaic System

Cited by 14 publications

References 58 publications

Photoinduced Charge Transfer Dynamics in the Carotenoid–Porphyrin–C₆₀ Triad via the Linearized Semiclassical Nonequilibrium Fermi’s Golden Rule

Photoinduced Charge Transfer Dynamics in the Carotenoid–Porphyrin–C₆₀ Triad via the Linearized Semiclassical Nonequilibrium Fermi’s Golden Rule

On the Interplay between Electronic Structure and Polarizable Force Fields When Calculating Solution-Phase Charge-Transfer Rates

Charge-Transfer Landscape Manifesting the Structure–Rate Relationship in the Condensed Phase Via Machine Learning

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Molecular-Level Exploration of the Structure-Function Relations Underlying Interfacial Charge Transfer in the Subphthalocyanine/ C60 Organic Photovoltaic System

Cited by 14 publications

References 58 publications

Photoinduced Charge Transfer Dynamics in the Carotenoid–Porphyrin–C60 Triad via the Linearized Semiclassical Nonequilibrium Fermi’s Golden Rule

Photoinduced Charge Transfer Dynamics in the Carotenoid–Porphyrin–C60 Triad via the Linearized Semiclassical Nonequilibrium Fermi’s Golden Rule

On the Interplay between Electronic Structure and Polarizable Force Fields When Calculating Solution-Phase Charge-Transfer Rates

Charge-Transfer Landscape Manifesting the Structure–Rate Relationship in the Condensed Phase Via Machine Learning

Contact Info

Product

Resources

About

Photoinduced Charge Transfer Dynamics in the Carotenoid–Porphyrin–C₆₀ Triad via the Linearized Semiclassical Nonequilibrium Fermi’s Golden Rule

Photoinduced Charge Transfer Dynamics in the Carotenoid–Porphyrin–C₆₀ Triad via the Linearized Semiclassical Nonequilibrium Fermi’s Golden Rule