The photodissociation of ozone: A quasi-classical approach to a quantum dynamics problem

Penfold, Thomas J.; Worth, Graham A.

doi:10.1016/j.jmgm.2007.01.012

Cited by 8 publications

(3 citation statements)

References 33 publications

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“…Among the most prominent examples are the quantum–classical Liouville equation, − the (linearized) path-integral representation of correlation functions, − nonadiabatic Bohmian dynamics, , the conditional wave function approach, as well as different revised versions of the Ehrenfest method − and of the surface-hopping scheme. − The latter are probably the most popular approaches as they can be easily implemented and combined with on-the-fly ab initio electronic structure calculations. − Ehrenfest dynamics, in its original mean-field formulation, may generate unphysical nuclear dynamics due to the impossibility to capture branching along different paths in configuration space. The stochastic nature of the surface-hopping algorithm, , instead, allows one to overcome this problem but still induces overcoherence effects based on an independent-trajectory approximation . As a consequence, a large amount of literature has been devoted to deal with the overcoherence problem of surface hopping in different ways. ,− …”

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“…The stochastic nature of the surface-hopping algorithm, 53,54 instead, allows one to overcome this problem but still induces overcoherence effects based on an independenttrajectory approximation. 55 As a consequence, a large amount of literature has been devoted to deal with the overcoherence problem of surface hopping in different ways. 44,56−62 Starting from the exact factorization of the electron−nuclear wave function, 63,64 an alternative trajectory-based algorithm to excited-state dynamics was recently proposed.…”

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Ab Initio Nonadiabatic Dynamics with Coupled Trajectories: A Rigorous Approach to Quantum (De)Coherence

Min

Agostini

Tavernelli

et al. 2017

J. Phys. Chem. Lett.

163

230

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We report the first nonadiabatic molecular dynamics study based on the exact factorization of the electron-nuclear wave function. Our approach (a coupled-trajectory mixed quantum-classical, CT-MQC, scheme) is based on the quantum-classical limit derived from systematic and controlled approximations to the full quantum-mechanical problem formulated in the exact-factorization framework. Its strength is the ability to correctly capture quantum (de)coherence effects in a trajectory-based approach to excited-state dynamics. We show this by benchmarking CT-MQC dynamics against a revised version of the popular fewest-switches surface-hopping scheme that is able to fix its well-documented overcoherence issue. The CT-MQC approach is successfully applied to investigation of the photochemistry (ring-opening) of oxirane in the gas phase, analyzing in detail the role of decoherence. This work represents a significant step forward in the establishment of the exact factorization as a powerful tool to study excited-state dynamics, not only for interpretation purposes but mainly for nonadiabatic ab initio molecular dynamics simulations.

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confidence: 99%

Ab Initio Nonadiabatic Dynamics with Coupled Trajectories: A Rigorous Approach to Quantum (De)Coherence

Min

Agostini

Tavernelli

et al. 2017

J. Phys. Chem. Lett.

163

230

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“…Comparison between TSH and QD has been performed previously and can be found within Refs. [37,38] and [20] (the latter also includes an external field). However, here, we pay particular attention to the comparison between the dynamics induced by the pulses calculated using LCT within the two approaches and rationalize the approximations.…”

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confidence: 99%

Local control theory in trajectory-based nonadiabatic dynamics

et al. 2011

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In this paper, we extend the implementation of nonadiabatic molecular dynamics within the framework of time-dependent density-functional theory in an external field described in Tavernelli et al. [Phys. Rev. A 81, 052508 (2010)] by calculating on-the-fly pulses to control the population transfer between electronic states using local control theory. Using Tully's fewest switches trajectory surface hopping method, we perform MD to control the photoexcitation of LiF and compare the results to quantum dynamics (QD) calculations performed within the Heidelberg multiconfiguration time-dependent Hartree package. We show that this approach is able to calculate a field that controls the population transfer between electronic states. The calculated field is in good agreement with that obtained from QD, and the differences that arise are discussed in detail. CURCHOD, PENFOLD, ROTHLISBERGER, AND TAVERNELLI PHYSICAL REVIEW A 84, 042507 (2011) * J (r; R)Ĥ el I (r; R)d r, (2.4) d J I,γ (R) are the first-order nonadiabatic coupling vectors, defined as d J I,γ (R) = * J (r; R)[∇ γ I (r; R)]d r, (2.5) and D J I,γ (R) are the second-order nonadiabatic coupling elements given by D J I,γ (R) = * J (r; R) ∇ 2 γ I (r; R) d r.(2.6)

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Nonadiabatic dynamics with trajectory surface hopping method

Barbatti

2011

WIREs Comput Mol Sci

437

427

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WOS:000296005000009International audienceThe trajectory surface hopping (TSH) method is a general methodology for dynamics propagation of nonadiabatic systems. It is based on the hypothesis that the time evolution of a wave packet through a potential-energy branching region can be approximated by an ensemble of independent semiclassical trajectories stochastically distributed among the branched surfaces. As it was proposed about 40 years ago, the TSH methodology has become one of the main tools for nonadiabatic dynamics propagation in molecular physics and chemistry. One reason for this success lies on its intuitive conceptual background allied to its high computational efficiency when compared to full quantum mechanical propagation. In this work, the TSH method is reviewed and applications from different fields are surveyed. (C) 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 1 620-633 DOI:10.1002/wcms.6

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The photodissociation of ozone: A quasi-classical approach to a quantum dynamics problem

Cited by 8 publications

References 33 publications

Ab Initio Nonadiabatic Dynamics with Coupled Trajectories: A Rigorous Approach to Quantum (De)Coherence

Ab Initio Nonadiabatic Dynamics with Coupled Trajectories: A Rigorous Approach to Quantum (De)Coherence

Local control theory in trajectory-based nonadiabatic dynamics

Nonadiabatic dynamics with trajectory surface hopping method

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