Variational nonadiabatic dynamics in the moving crude adiabatic representation: Further merging of nuclear dynamics and electronic structure

Joubert-Doriol, Loïc; Izmaylov, Artur F.

doi:10.1063/1.5020655

Cited by 16 publications

(23 citation statements)

References 58 publications

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“…New developments merging the ideas of vMCG, Ehrenfest dynamics, and the Exact Factorization are ongoing . The idea of moving beyond the use of a purely adiabatic electronic basis with traveling Gaussian functions has triggered interesting new work in the last years . Considerable efforts have been invested more recently in developing a robust algorithm for performing MCTDH on‐the‐fly .…”

Section: Discussionmentioning

confidence: 99%

“…155 The idea of moving beyond the use of a purely adiabatic electronic basis with traveling Gaussian functions has triggered interesting new work in the last years. [156][157][158][159] Considerable efforts have been invested more recently in developing a robust algorithm for performing MCTDH on-the-fly. 160 Nonadiabatic molecular dynamics combined with machine-learning strategies for the calculation of electronic-structure quantities has recently emerged.…”

Section: Discussionmentioning

confidence: 99%

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Different flavors of nonadiabatic molecular dynamics

Agostini

Curchod

2019

WIREs Comput Mol Sci

100

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The Born‐Oppenheimer approximation constitutes a cornerstone of our understanding of molecules and their reactivity, partly because it introduces a somewhat simplified representation of the molecular wavefunction. However, when a molecule absorbs light containing enough energy to trigger an electronic transition, the simplistic nature of the molecular wavefunction offered by the Born‐Oppenheimer approximation breaks down as a result of the now non‐negligible coupling between nuclear and electronic motion, often coined nonadiabatic couplings. Hence, the description of nonadiabatic processes implies a change in our representation of the molecular wavefunction, leading eventually to the design of new theoretical tools to describe the fate of an electronically‐excited molecule. This Overview focuses on this quantity—the total molecular wavefunction—and the different approaches proposed to describe theoretically this complicated object in non‐Born‐Oppenheimer conditions, namely the Born‐Huang and Exact‐Factorization representations. The way each representation depicts the appearance of nonadiabatic effects is then revealed by using a model of a coupled proton–electron transfer reaction. Applying approximations to the formally exact equations of motion obtained within each representation leads to the derivation, or proposition, of different strategies to simulate the nonadiabatic dynamics of molecules. Approaches like quantum dynamics with fixed and time‐dependent grids, traveling basis functions, or mixed quantum/classical like surface hopping, Ehrenfest dynamics, or coupled‐trajectory schemes are described in this Overview. This article is categorized under: Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics Software > Simulation Methods Theoretical and Physical Chemistry > Spectroscopy

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Different flavors of nonadiabatic molecular dynamics

Agostini

Curchod

2019

WIREs Comput Mol Sci

100

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“…[47][48][49] We should emphasize that historically, the QD scheme was introduced to propagate the electronic amplitudes in surface hopping simulations, which is commonly referred as the "local diabatic" basis approach. 18,61,62,64,65 It has also been used in scattering probability calculations 66 and recently, gaussian wave packet dynamics approaches, [67][68][69][70][71] and is referred as the "moving crude adiabatic" scheme. 71 In the QD propagation scheme, we expand the scope of this idea by using it as a general framework to interface any diabatic trajectory-based dynamics methods with routinely available adiabatic electronic structure information.…”

Section: Theoretical Approachmentioning

confidence: 99%

“…18,61,62,64,65 It has also been used in scattering probability calculations 66 and recently, gaussian wave packet dynamics approaches, [67][68][69][70][71] and is referred as the "moving crude adiabatic" scheme. 71 In the QD propagation scheme, we expand the scope of this idea by using it as a general framework to interface any diabatic trajectory-based dynamics methods with routinely available adiabatic electronic structure information. Thus, it opens up many possibilities to use recently developed di-abatic dynamics methods 38,39,41,42,44,72,73 for nonadiabatic on-the-fly simulations.…”

Section: Theoretical Approachmentioning

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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“…Because of the readily available electronic structure information in the adiabatic representation, quantum dynamics approaches formulated in this representation have been extensively used to perform on-the-fly NAMD simulations, including the popular fewest-switches surface hopping (FSSH) (4,(8)(9)(10)(11)(12)(13)(14)(15), ab-initio multiple spawning (AIMS) (3,7,16), and several recently developed Gaussian wavepacket approaches (17)(18)(19)(20)(21), coupled-trajectory approaches (22)(23)(24)(25), and the ab-initio multiconfiguration time-dependent Hartree (MCTDH) (26,27). Among them, FSSH is one of the most popular approaches in NAMD, which uses mixed quantum-classical (MQC) treatment of the electronic and nuclear DOFs that provides efficient non-adiabatic simulation.…”

mentioning

confidence: 99%

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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Variational nonadiabatic dynamics in the moving crude adiabatic representation: Further merging of nuclear dynamics and electronic structure

Cited by 16 publications

References 58 publications

Different flavors of nonadiabatic molecular dynamics

Different flavors of nonadiabatic molecular dynamics

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

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

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