Accelerated Molecular Dynamics Study of Z/E Isomerization of Azobenzene: Kramers’ Theory Validation

Shigemitsu, Yasuhiro; Ohga, Yasushi

doi:10.1007/s10953-014-0237-5

Cited by 2 publications

(3 citation statements)

References 27 publications

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“…[86]. Shigemitsu and Ohga [87] used PGH theory to analyze molecular dynamics simulations of the isomerization of azobenzene, however, their central conclusion was that in reality, the reaction occurs in the spatial diffusion-limited regime so that the turnover theory as such is not really that important.…”

Section: Simulations Of Reactions In Liquidsmentioning

confidence: 99%

“…The turnover has been observed experimentally using levitated nanoparticles [22] . It is at the center of attempts at understanding reactions in microcavities [23–25] and there have been numerous reports on its observation in reactions in liquids [26–30] . It has also been used to gain insight into measured hopping distributions in studies of surface diffusion [31–34] …”

Section: Introductionmentioning

confidence: 99%

“…[22] It is at the center of attempts at understanding reactions in microcavities [23][24][25] and there have been numerous reports on its observation in reactions in liquids. [26][27][28][29][30] It has also been used to gain insight into measured hopping distributions in studies of surface diffusion. [31][32][33][34] This long introduction should hopefully draw the reader deeper into the turnover problem.…”

Section: Introductionmentioning

confidence: 99%

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Recent Developments in Kramers’ Theory of Reaction Rates

Pollak

Miret‐Artés

2023

ChemPhysChem

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In this short review, we provide an update of recent developments in Kramers’ theory of reaction rates. After a brief introduction stressing the importance of this theory initially developed for chemical reactions, we briefly present the main theoretical formalism starting from the generalized Langevin equation and continue by showing the main points of the modern Pollak, Grabert and Hänggi theory. Kramers’ theory is then sketched for quantum and classical surface diffusion. As an illustration the surface diffusion of Na atoms on a Cu(110) surface is discussed showing escape rates, jump distributions and diffusion coefficients as a function of reduced friction. Finally, some very recent applications of turnover theory to different fields such as nanoparticle levitation, microcavity polariton dynamics and simulation of reaction in liquids are presented. We end with several open problems and future challenges faced up by Kramers turnover theory.

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Section: Simulations Of Reactions In Liquidsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Recent Developments in Kramers’ Theory of Reaction Rates

Pollak

Miret‐Artés

2023

ChemPhysChem

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A personal perspective of the present status and future challenges facing thermal reaction rate theory

Pollak

2024

The Journal of Chemical Physics

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Reaction rate theory has been at the center of physical chemistry for well over one hundred years. The evolution of the theory is not only of historical interest. Reliable and accurate computation of reaction rates remains a challenge to this very day, especially in view of the development of quantum chemistry methods, which predict the relevant force fields. It is still not possible to compute the numerically exact rate on the fly when the system has more than at most a few dozen anharmonic degrees of freedom, so one must consider various approximate methods, not only from the practical point of view of constructing numerical algorithms but also on conceptual and formal levels. In this Perspective, I present some of the recent analytical results concerning leading order terms in an ℏ2m series expansion of the exact rate and their implications on various approximate theories. A second aspect has to do with the crossover temperature between tunneling and thermal activation. Using a uniform semiclassical transmission probability rather than the “primitive” semiclassical theory leads to the conclusion that there is no divergence problem associated with a “crossover temperature.” If one defines a semiclassical crossover temperature as the point at which the tunneling energy of the instanton equals the barrier height, then it is a factor of two higher than its previous estimate based on the “primitive” semiclassical approximation. In the low temperature tunneling regime, the uniform semiclassical theory as well as the “primitive” semiclassical theory were based on the classical Euclidean action of a periodic orbit on the inverted potential. The uniform semiclassical theory wrongly predicts that the “half-point,” which is the energy at which the transmission probability equals 1/2, for any barrier potential, is always the barrier energy. We describe here how augmenting the Euclidean action with constant terms of order ℏ2 can significantly improve the accuracy of the semiclassical theory and correct this deficiency. This also leads to a deep connection with and improvement of vibrational perturbation theory. The uniform semiclassical theory also enables an extension of the quantum version of Kramers’ turnover theory to temperatures below the “crossover temperature.” The implications of these recent advances on various approximate methods used to date are discussed at length, leading to the conclusion that reaction rate theory will continue to challenge us both on conceptual and practical levels for years to come.

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Accelerated Molecular Dynamics Study of Z/E Isomerization of Azobenzene: Kramers’ Theory Validation

Cited by 2 publications

References 27 publications

Recent Developments in Kramers’ Theory of Reaction Rates

Recent Developments in Kramers’ Theory of Reaction Rates

A personal perspective of the present status and future challenges facing thermal reaction rate theory

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