Nonadiabatic Chemical Dynamics: Comprehension and Control of Dynamics, and Manifestation of Molecular Functions

Nakamura, Hiroki

doi:10.1002/9780470259474.ch3

Cited by 18 publications

(14 citation statements)

References 167 publications

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“…Fortunately, however, ρ 3D τ is proportional to ρ 2D t+δ t (see Eqs. (39), (40), and (44)) and thus, also to ρ C t+δ t , ensuring thereby the accuracy of the (renormalized) planar SCWT.…”

Section: F Inability Of Classical Mechanics To Propagate ρ 3d τmentioning

confidence: 91%

“…by deriving expressions in the same spirit as Eqs. (39) and (40). This task, however, does not seem to be simple.…”

Section: E Scw Formula For the Planar Motionmentioning

confidence: 99%

“…For simplicity's sake, however, we ignored this fact, focusing our attention on SCWT for fragmentations taking place adiabatically on single excited electronic states. SCWT, however, can be straightforwardly extended to processes involving nonadiabatic transitions by using several approaches, like the Landau-Zener-Stueckelberg model, 39 its extension by Zhu and Nakamura, 40 or the surface hopping method of Tully 41,42 (this is not an exhaustive list).…”

Section: Application To the Photodissociation Of Methyl Iodidementioning

confidence: 99%

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Semiclassical Wigner theory of photodissociation in three dimensions: Shedding light on its basis

Arbelo-González

Bonnet

Garcı́a-Vela

2015

The Journal of Chemical Physics

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The semiclassical Wigner theory (SCWT) of photodissociation dynamics, initially proposed by Brown and Heller [J. Chem. Phys. 75, 186 (1981)] in order to describe state distributions in the products of direct collinear photodissociations, was recently extended to realistic three-dimensional triatomic processes of the same type [Arbelo-González et al., Phys. Chem. Chem. Phys. 15, 9994 (2013)]. The resulting approach, which takes into account rotational motions in addition to vibrational and translational ones, was applied to a triatomic-like model of methyl iodide photodissociation and its predictions were found to be in nearly quantitative agreement with rigorous quantum results, but at a much lower computational cost, making thereby SCWT a potential tool for the study of polyatomic reaction dynamics. Here, we analyse the main reasons for this agreement by means of an elementary model of fragmentation explicitly dealing with the rotational motion only. We show that our formulation of SCWT makes it a semiclassical approximation to an approximate planar quantum treatment of the dynamics, both of sufficient quality for the whole treatment to be satisfying.

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Section: F Inability Of Classical Mechanics To Propagate ρ 3d τmentioning

confidence: 91%

“…by deriving expressions in the same spirit as Eqs. (39) and (40). This task, however, does not seem to be simple.…”

Section: E Scw Formula For the Planar Motionmentioning

confidence: 99%

Section: Application To the Photodissociation Of Methyl Iodidementioning

confidence: 99%

See 1 more Smart Citation

Semiclassical Wigner theory of photodissociation in three dimensions: Shedding light on its basis

Arbelo-González

Bonnet

Garcı́a-Vela

2015

The Journal of Chemical Physics

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“…This allows the same approximate formulas to be used in both settings. Despite the many different developments that are based on ZNT [22,23] and the claim that the theory comprises a complete solution to curve-crossing problems, there seems to be only few articles in the literature that deal with the basic characteristics of the theory. Also, the applicability of the theory must be, in principle, considered for each model independently due to the phenomenological character of the theory.…”

Section: Introductionmentioning

confidence: 99%

Zhu-Nakamura theory and the superparabolic level-glancing models

Lehto

2013

Phys. Rev. A

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We study the applicability of the Zhu-Nakamura theory to a class of time-dependent quantum mechanical level-crossing models called superparabolic level-glancing models. The phenomenon of a level glancing, being on the borderline between a proper crossing of energy levels and an avoided crossing, is also an important special case between the two different approximative expressions in the Zhu-Nakamura theory. It is seen that the application of the theory to these models is not straightforward. We discuss some possible causes of these difficulties and also compare the approximative formulas of Zhu-Nakamura theory to those obtained by the generalization of the DDP theory.Comment: 10 pages, 3 figure

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“…8,9 Elucidating the mechanisms and rates for these processes remains a critical challenge from both the theoretical and experimental perspectives.…”

Section: Introductionmentioning

confidence: 99%

Exact quantum statistics for electronically nonadiabatic systems using continuous path variables

Ananth

Miller

2010

The Journal of Chemical Physics

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We derive an exact, continuous-variable path integral (PI) representation of the canonical partition function for electronically nonadiabatic systems. Utilizing the Stock-Thoss (ST) mapping for an N -level system, matrix elements of the Boltzmann operator are expressed in Cartesian coordinates for both the nuclear and electronic degrees of freedom. The PI discretization presented here properly constrains the electronic Cartesian coordinates to the physical subspace of the mapping. We numerically demonstrate that the resulting PI-ST representation is exact for the calculation of equilibrium properties of systems with coupled electronic and nuclear degrees of freedom. We further show that the PI-ST formulation provides a natural means to initialize semiclassical trajectories for the calculation of real-time thermal correlation functions, which is numerically demonstrated in applications to a series of nonadiabatic model systems.

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Nonadiabatic Chemical Dynamics: Comprehension and Control of Dynamics, and Manifestation of Molecular Functions

Cited by 18 publications

References 167 publications

Semiclassical Wigner theory of photodissociation in three dimensions: Shedding light on its basis

Semiclassical Wigner theory of photodissociation in three dimensions: Shedding light on its basis

Zhu-Nakamura theory and the superparabolic level-glancing models

Exact quantum statistics for electronically nonadiabatic systems using continuous path variables

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