Surface-hopping trajectory calculations of collision-induced dissociation processes with and without charge transfer

Kuntz, P. J.; Kendrick, John; Whitton, W.N.

doi:10.1016/0301-0104(79)85058-2

Cited by 60 publications

(29 citation statements)

References 36 publications

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“…The second class of surface hopping methods, the semiclassical approach, includes methods in which the state transition is modeled by probabilities derived from the WKB semiclassical wavefunction Ansatz, [113][114][115][116][117] as the Landau-Zener probability for instance. [118][119][120] In contrast to FSSH probabilities (Eq.…”

Section: Alternatives To Fewest-switches Probabilitymentioning

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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Section: Alternatives To Fewest-switches Probabilitymentioning

confidence: 99%

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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“…Their examples make it especially clear that maintaining coherence over an entire trajectory can lead to significant errors. One classical path method that was developed with this kind of consideration as a motivation is the surface hopping method of Parlant and Gislason, 13,14 which differs from an earlier method of Kuntz et al 15 in the prescription for calculating the hopping probability and from an earlier method of Blais and Truhlar 16 in its insistence on coherent evolution through each "complete passage" 1a of a strong coupling region. This method, therefore, mitigates some of the decoherence that arises (in other TSH methods) from surface hops within strongly coupled regions as well as the inaccuracies explained by Thachuk et al 12 The methods discussed so far are independent trajectory methods.…”

Section: Introductionmentioning

confidence: 99%

Coherent switching with decay of mixing: An improved treatment of electronic coherence for non-Born–Oppenheimer trajectories

Zhu

Nangia

Jasper

et al. 2004

The Journal of Chemical Physics

323

427

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Abstract. The self-consistent decay of mixing (SCDM) semiclassical trajectory method for electronically nonadiabatic dynamics is improved by modifying the switching probability that determines the instantaneous electronic state toward which the system decoheres. The new method is called coherent switching with decay of mixing (CSDM), and it differs from the previously presented SCDM method in that the electronic amplitudes controlling the switching of the decoherent state are treated fully coherently in the electronic equations of motion for each complete passage through a strong interaction region. The new method is tested against accurate quantum mechanical calculations for twelve atom-diatom scattering test cases. Also tested are the SCDM method and the trajectory surface hopping method of Parlant and Gislason that requires coherent passages through each strong interaction region, and which we call the ECP-TSH method. The results are compared with previously presented results for the fewest-switches with time uncertainty and Tully's fewest switches (TFS) surface hopping methods and the semiclassical Ehrenfest method. We find that the CSDM method is the most accurate of the semiclassical trajectory methods tested. Including coherent passages improves the accuracy of the SCDM method (i.e., the CSDM method is more accurate than the SCDM method) but not of the trajectory surface hopping method (i.e., the ECP-TSH method is not more accurate on average than the TFS method).

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“…1,2,4,19,20 The present article is primarily concerned with developing and testing semiclassical methods for atommolecule collisions in the latter, less studied case. In particular we focus on the trajectory surface hopping [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] ͑TSH͒ method and specifically on Tully's fewest-switches ͑TFS͒ algorithm 6,30 for surface hopping. ͑TFS is also called molecular dynamics with quantum transitions or MDQT.͒ Surface hopping is an ad hoc addition to classical mechanics in which trajectories instantaneously switch electronic states, i.e., the potential energy function that determines the nuclear motion is discontinuous.…”

Section: Introductionmentioning

confidence: 99%

The treatment of classically forbidden electronic transitions in semiclassical trajectory surface hopping calculations

Jasper

Hack

Truhlar

2001

The Journal of Chemical Physics

124

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A family of four weakly coupled electronically nonadiabatic bimolecular model photochemical systems is presented. Fully converged quantum mechanical calculations with up to 25 269 basis functions were performed for full-dimensional atom-diatom collisions to determine the accurate scattering dynamics for each of the four systems. The quantum mechanical probabilities for electronically nonadiabatic reaction and for nonreactive electronic deexcitation vary from 10 Ϫ1 to 10 Ϫ5 . Tully's fewest-switches ͑TFS͒ semiclassical trajectory surface-hopping method ͑also called molecular dynamics with quantum transitions or MDQT͒ is tested against the accurate quantal results. The nonadiabatic reaction and nonreactive deexcitation events are found to be highly classically forbidden for these systems, which were specifically designed to model classically forbidden electronic transitions ͑also called frustrated hops͒. The TFS method is shown to systematically overestimate the nonadiabatic transition probabilities due to the high occurrence of frustrated hops. In order to better understand this problem and learn how to best minimize the errors, we test several variants of the TFS method on the four new weakly coupled systems and also on a set of three more strongly coupled model systems that have been presented previously. The methods tested here differ from one another in their treatment of the classical trajectory during and after a frustrated hopping event. During the hopping event we find that using a rotated hopping vector results in the best agreement of semiclassical and quantal results for the nonadiabatic transition probabilities. After the hopping event, we find that ignoring frustrated hops instead of reversing the momentum along the nonadiabatic coupling vector results in the best agreement with the accurate quantum results for the final vibrational and rotational moments. We also test the use of symmetrized probabilities in the equations for the TFS hopping probabilities. These methods systematically lead to increased error for systems with weakly coupled electronic states unless the hopping probabilities are symmetrized according to the electronic state populations.

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Surface-hopping trajectory calculations of collision-induced dissociation processes with and without charge transfer

Cited by 60 publications

References 36 publications

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Coherent switching with decay of mixing: An improved treatment of electronic coherence for non-Born–Oppenheimer trajectories

The treatment of classically forbidden electronic transitions in semiclassical trajectory surface hopping calculations

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