Some New Classical and Semiclassical Models for Describing Tunneling Processes with Real-Valued Classical Trajectories

Xing, Jianhua; Coronado, Eduardo A.; Miller, William H.

doi:10.1021/jp0046086

Cited by 14 publications

(7 citation statements)

References 73 publications

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“…[132,[136][137][138][139][140][141][142][143][144][145][146][147][148][149][150][151][152][153] Tunneling effects can also not be described with surface hopping although there exist several approaches to alleviate this deficiency, see, for example, Refs. [154][155][156][157][158].…”

Section: Dynamics Simulations Of Intersystem Crossingmentioning

confidence: 99%

“…The latter effect can be partially mitigated using so-called decoherence corrections; the interested reader is referred to the according literature. 132,[136][137][138][139][140][141][142][143][144][145][146][147][148][149][150][151][152][153] Tunneling effects can also not be described with surface hopping although there exist several approaches to alleviate this deficiency, see, e.g., references [154][155][156][157][158] .…”

Section: Dynamics Simulations Of Intersystem Crossingmentioning

confidence: 99%

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A general method to describe intersystem crossing dynamics in trajectory surface hopping

Mai

Marquetand

González

2015

Int J of Quantum Chemistry

271

406

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Intersystem crossing is a radiationless process that can take place in a molecule irradiated by UV‐Vis light, thereby playing an important role in many environmental, biological and technological processes. This paper reviews different methods to describe intersystem crossing dynamics, paying attention to semiclassical trajectory theories, which are especially interesting because they can be applied to large systems with many degrees of freedom. In particular, a general trajectory surface hopping methodology recently developed by the authors, which is able to include nonadiabatic and spin‐orbit couplings in excited‐state dynamics simulations, is explained in detail. This method, termed SHARC, can in principle include any arbitrary coupling, what makes it generally applicable to photophysical and photochemical problems, also those including explicit laser fields. A step‐by‐step derivation of the main equations of motion employed in surface hopping based on the fewest‐switches method of Tully, adapted for the inclusion of spin‐orbit interactions, is provided. Special emphasis is put on describing the different possible choices of the electronic bases in which spin‐orbit can be included in surface hopping, highlighting the advantages and inconsistencies of the different approaches. © 2015 Wiley Periodicals, Inc.

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Section: Dynamics Simulations Of Intersystem Crossingmentioning

confidence: 99%

Section: Dynamics Simulations Of Intersystem Crossingmentioning

confidence: 99%

A general method to describe intersystem crossing dynamics in trajectory surface hopping

Mai

Marquetand

González

2015

Int J of Quantum Chemistry

271

406

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“…7,8 Although it is sometimes possible to overcome this difficulty by an analysis which provides optimal values for the parameters, 7 this approach has been implemented only for the one-dimensional ͑1D͒ Eckart potential and its application to more general systems seems difficult. A number of additional ways to describe tunneling within the framework of HK-like approximations have been proposed [9][10][11][12][13][14][15][16][17][18] but, in most cases, it is not clear whether they are sufficiently general and numerically efficient for the practical treatment of tunneling in multidimensional systems in the absence of thermal averaging.…”

Section: Tunneling In Two-dimensional Systems Using a Higher-order Hementioning

confidence: 99%

Tunneling in two-dimensional systems using a higher-order Herman–Kluk approximation

Hochman

Kay

2009

The Journal of Chemical Physics

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A principal weakness of the Herman–Kluk (HK) semiclassical approximation is its failure to provide a reliably accurate description of tunneling between different classically allowed regions. It was previously shown that semiclassical corrections significantly improve the HK treatment of tunneling for the particular case of the one-dimensional Eckart system. Calculations presented here demonstrate that the lowest-order correction also substantially improves the HK description of tunneling across barriers in two-dimensional systems. Numerical convergence issues either do not arise or are easily overcome, so that the calculations require only a moderate number of ordinary, real, classical trajectories.

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“…A general and popular alternative to quantum scattering approaches is the quasi-classical trajectory (QCT) method. − This approach may provide nearly quantitative results if semiclassically corrected to account for possible quantum effects such as, mainly, (i) tunneling, − (ii) nonadiabatic transitions, − or (iii) the quantization of internal product motions, approximately achieved by means of Gaussian binning (GB). − As compared with quantum scattering calculations, QCT calculations are very friendly. Moreover, they allow the study of polyatomic reactions in full-dimensionality. − Last but not least, the QCT method is a powerful tool for revealing reaction mechanisms. , …”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Barrierless Chemical Reactions Involving Nearly Elastic Rebound: The Case of S(¹D) + X₂, X = H, D

et al. 2019

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For some values of the total angular momentum consistent with reaction, the title processes involve nonreactive trajectories proceeding through a single rebound mechanism during which the internal motion of the reagent diatom is nearly unperturbed. When such paths are in a significant amount, the classical reaction probability is found to be markedly lower than the quantum mechanical one. This finding was recently attributed to an unusual quantum effect called diffraction-mediated trapping, and a semiclassical correction was proposed in order to take into account this effect in the classical trajectory method. In the present work, we apply the resulting approach to the calculation of opacity functions as well as total and state-resolved integral cross sections (ICSs) and compare the values obtained with exact quantum ones, most of which are new. As the title reactions proceed through a deep insertion well, mean potential statistical calculations are also presented. Seven values of the collision energy, ranging from 30 to 1127 K, are considered. Two remarkable facts stand out: (i) The corrected classical treatment strongly improves the accuracy of the opacity function as compared to the usual classical treatment. When the entrance transition state is tight, however, those trajectories crossing it with a bending vibrational energy below the zero point energy must be discarded. (ii) The quantum opacity function, particularly its cutoff, is finely reproduced by the statistical approach. Consequently, the total ICS is also very well described by the two previous approximate methods. These, however, do not predict state-resolved ICSs with the same accuracy, proving thereby that (i) one or several genuine quantum effects involved in the dynamics are missed by the corrected classical treatment and (ii) the dynamics are not fully statistical.

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Some New Classical and Semiclassical Models for Describing Tunneling Processes with Real-Valued Classical Trajectories

Cited by 14 publications

References 73 publications

A general method to describe intersystem crossing dynamics in trajectory surface hopping

A general method to describe intersystem crossing dynamics in trajectory surface hopping

Tunneling in two-dimensional systems using a higher-order Herman–Kluk approximation

Theoretical Study of Barrierless Chemical Reactions Involving Nearly Elastic Rebound: The Case of S(¹D) + X₂, X = H, D

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Some New Classical and Semiclassical Models for Describing Tunneling Processes with Real-Valued Classical Trajectories

Cited by 14 publications

References 73 publications

A general method to describe intersystem crossing dynamics in trajectory surface hopping

A general method to describe intersystem crossing dynamics in trajectory surface hopping

Tunneling in two-dimensional systems using a higher-order Herman–Kluk approximation

Theoretical Study of Barrierless Chemical Reactions Involving Nearly Elastic Rebound: The Case of S(1D) + X2, X = H, D

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Theoretical Study of Barrierless Chemical Reactions Involving Nearly Elastic Rebound: The Case of S(¹D) + X₂, X = H, D