Investigating photoinduced proton coupled electron transfer reaction using quasi diabatic dynamics propagation

Mandal, Arkajit; Shakib, Farnaz A.; Huo, Pengfei

doi:10.1063/1.5030634

Cited by 29 publications

(41 citation statements)

References 105 publications

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“…With the nuclear geometry closely following the reference geometry at every single propagation step, the QD basis forms a convenient and compact basis in each short-time propagation segment. To summarize, the QD scheme (40,41,48,49) uses the adiabatic states associated with a reference geometry as the quasi-diabatic states during a short-time quantum propagation, and dynamically update the definition of the QD states along the time-dependent nuclear trajectory. It allows a seamless interface between diabatic dynamics approaches with adiabatic electronic structure calculations.…”

Section: Significance Statementmentioning

confidence: 99%

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Quasi-Diabatic Scheme for Nonadiabatic On-the-Fly Simulations

Zhou

Mandal

Huo

2019

J. Phys. Chem. Lett.

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We use the quasi-diabatic (QD) propagation scheme to perform onthe-fly non-adiabatic simulations of the photodynamics of ethylene. The QD scheme enables a seamless interface between accurate diabatic-based quantum dynamics approaches and adiabatic electronic structure calculations, explicitly avoiding any efforts to construct global diabatic states or reformulate the diabatic dynamics approach to the adiabatic representation. Using partial linearized path-integral approach and symmetrical quasi-classical approach as the diabatic dynamics methods, the QD propagation scheme enables direct non-adiabatic simulation with the CASSCF on-the-fly electronic structure calculations. The population dynamics obtained from both approaches are in a close agreement with the quantum wavepacket based method and outperform the widely used trajectory surface hopping approach. Further analysis on the ethylene photodeactivation pathways demonstrates the correct predictions of competing processes of non-radiative relaxation mechanism through various conical intersections. This work provides the foundation of using accurate diabatic dynamics approaches and on-the-fly adiabatic electronic structure information to perform ab-initio non-adiabatic simulation.Non-adiabatic on-the-fly simulation | Quasi-Diabatic scheme | Diabatic dynamics approach | Path-integral methods

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Section: Significance Statementmentioning

confidence: 99%

“…We emphasize that Eqn. 6 includes derivatives with respect to all possible sources of the nuclear dependence, including those from the adiabatic potentials as well as the adiabatic states (48,49). The details of this justification is provided in the SI.…”

Section: Potential and Gradient Matrix Elements In The Quasi-diabaticmentioning

confidence: 99%

Quasi-Diabatic Scheme for Nonadiabatic On-the-Fly Simulations

Zhou

Mandal

Huo

2019

J. Phys. Chem. Lett.

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“…To model the condensed phase PCET reaction, the collective solvent mode R is usually coupled to an additional harmonic bath 21,43,54 througĥ…”

Section: Pcet Model Hamiltonianmentioning

confidence: 99%

“…Instead, the solvent fluctuations induced by {R ζ } are modeled with non-zero initial momentum 18 associated with the R. We emphasize that there is no additional theoretical challenge to incorporateĤ sb into the QD propagations outlined in this paper, as it has been done in our previous work. 54 In this study, we treat both the electron and the proton quantum mechanically by using the adiabatic vibronic states {|Φ α (R) }. These states are defined as the eigenstates of the following quantum-part of the Hamiltonian operator…”

Section: Pcet Model Hamiltonianmentioning

confidence: 99%

Quasi-Diabatic Propagation Scheme for Direct Simulation of Proton-Coupled Electron Transfer Reaction

Mandal

Shakib

et al. 2019

J. Phys. Chem. A

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We apply a recently-developed quasi-diabatic (QD) propagation scheme to simulate proton-coupled electron transfer (PCET) reactions. This scheme enables a direct interface between an accurate diabatic dynamics approach and the adiabatic vibronic states. It explicitly avoids theoretical efforts to pre-construct diabatic states for the transferring electron and proton or reformulate diabatic dynamics methods to the adiabatic representation, both of which are non-trivial tasks. Using partial linearized path-integral approach and symmetrical quasi-classical approach as the diabatic dynamics methods, we demonstrate that the QD propagation scheme provides accurate vibronic dynamics of PCET reactions and reliably predict the correct reaction mechanism without any a priori assumptions. This work demonstrates the possibility to directly simulate challenging PCET reactions by using accurate diabatic dynamics approaches and adiabatic vibronic information.

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“…39,40 PLDM is an approximate real-time path-integral approach that has been successfully applied to investigate various nonadiabatic processes. [41][42][43][44][45] A brief summary of this approach, together with the numerical details of the simulations are provided in the Supporting Information.…”

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confidence: 99%