An exact factorization perspective on quantum interferences in nonadiabatic dynamics

Curchod, Basile F. E.; Agostini, Federica; Gross, E. K. U.

doi:10.1063/1.4958637

Cited by 49 publications

(57 citation statements)

References 99 publications

(145 reference statements)

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“…Regions where the TDPES is large are associated to regions where the nuclear density is small (tending towards a node), whereas the series of minima observed in the TDPES (at around x = 3.9 and for y varying between -0.5 and 0.3) creates a multi-peaked nuclear density. The oscillatory features of the TDPES in the strong-coupling case can be interpreted as a two-dimensional generalization of our previous analysis [51] on the effect of interferences on the TDPES. From Figure 2 (middle panel) it is evident that when the nuclear wavepacket moving on S 1 reaches the CI, it transfers population to S 0 .…”

Section: Time-dependent Potential Energy Surface -(R T)supporting

confidence: 63%

When the exact factorization meets conical intersections...

Agostini

Curchod

2018

Eur. Phys. J. B

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Capturing nuclear dynamics through conical intersections is pivotal to understand the fate of photoexcited molecules. The concept of a conical intersection, however, belongs to a specific definition of the electronic states, within a Born-Huang representation of the molecular wavefunction. How would these ultrafast funneling processes be translated if an exact factorization of the molecular wavefunction were to be used? In this article, we build upon our recent analysis [B.F.E. Curchod, F. Agostini, J. Phys. Chem. Lett. 8, 831 (2017)] and address this question in a broader perspective by studying the dynamics of a nuclear wavepacket through two types of conical intersections, differing by the strength of their underlying diabatic coupling. Our results generalize our previous findings by (i) showing that the time-dependent potential energy surface smoothly varies, both in time and in position, between the corresponding diabatic and adiabatic potentials, with sometimes more complex features if interferences are observed, (ii) highlighting the non-trivial behavior of the time-dependent vector potential and the fact that it cannot be gauged away in general, and (iii) justifying some approximations employed in the derivation of a mixed quantum/classical scheme based on the exact factorization.

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Section: Time-dependent Potential Energy Surface -(R T)supporting

confidence: 63%

When the exact factorization meets conical intersections...

Agostini

Curchod

2018

Eur. Phys. J. B

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“…The EF provides a framework to analyze the nuclear-electron coupling within static and dynamical approaches, [138][139][140][141][142][143] allowing the definition of new NA-MQC dynamics methods. [144][145] This is the case of the recently developed coupled-trajectory MQC (CT-MQC), 10,[146][147][148] which shares some similarities with the traditional Ehrenfest method.…”

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confidence: 99%

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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Nonadiabatic mixed quantum-classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution of nonadiabatic phenomena in molecules and supramolecular assemblies. NA-MQC is characterized by a partition of the molecular system into two subsystems: one to be treated quantum mechanically (usually but not restricted to electrons) and another to be dealt with classically (nuclei). The two subsystems are connected through nonadiabatic couplings terms to enforce self-consistency. A local approximation underlies the classical subsystem, implying that direct dynamics can be simulated, without needing precomputed potential energy surfaces. The NA-MQC split allows reducing computational costs, enabling the treatment of realistic molecular systems in diverse fields. Starting from the three most well-established methods-mean-field Ehrenfest, trajectory surface hopping, and multiple spawning-this review focuses on the NA-MQC dynamics methods and programs developed in the last 10 years. It stresses the relations between approaches and their domains of application. The electronic structure methods most commonly used together with NA-MQC dynamics are reviewed as well. The accuracy and precision of NA-MQC simulations are critically discussed, and general guidelines to choose an adequate method for each application are delivered.

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“…The explicit time-dependence of the electronic wavefunction results in a potential energy surface that depends on both nuclear coordinates and time, as well as a time-dependent vector potential 32,[71][72][73][74][75][76]. Unlike the BOA ansatz, the electronic wavefunction is time-dependent.…”

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confidence: 99%

Ab Initio Nonadiabatic Quantum Molecular Dynamics

2018

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The Born-Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approximation breaks down when the dynamics of molecules in excited electronic states are considered. Describing dynamics when the Born-Oppenheimer approximation breaks down requires a quantum mechanical description of the nuclei. Chemical reaction dynamics on excited electronic states is critical for many applications in renewable energy, chemical synthesis, and bioimaging. Furthermore, it is necessary in order to connect with many ultrafast pump-probe spectroscopic experiments. In this review, we provide an overview of methods that can describe nonadiabatic dynamics, with emphasis on those that are able to simultaneously address the quantum mechanics of both electrons and nuclei. Such ab initio quantum molecular dynamics methods solve the electronic Schrödinger equation alongside the nuclear dynamics and thereby avoid the need for precalculation of potential energy surfaces and nonadiabatic coupling matrix elements. Two main families of methods are commonly employed to simulate nonadiabatic dynamics in molecules: full quantum dynamics, such as the multiconfigurational time-dependent Hartree method, and classical trajectory-based approaches, such as trajectory surface hopping. In this review, we describe a third class of methods that is intermediate between the two: Gaussian basis set expansions built around trajectories.

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An exact factorization perspective on quantum interferences in nonadiabatic dynamics

Cited by 49 publications

References 99 publications

When the exact factorization meets conical intersections...

When the exact factorization meets conical intersections...

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Ab Initio Nonadiabatic Quantum Molecular Dynamics

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