Quantum diffusive dynamics of macromolecular transitions

We study the role of quantum fluctuations of atomic nuclei in the real-time dynamics of non-equilibrium macro-molecular transitions. To this goal we introduce an extension of the dominant reaction pathways formalism, in which the quantum corrections to the classical overdamped Langevin dynamics are...

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Bibliographic Details
Published in:The Journal of chemical physics 2011-07, Vol.135 (3), p.034103-034103-11
Main Authors: Beccara, S. a, Garberoglio, G., Faccioli, P.
Format: Article
Language:English
Subjects:
Diffusion
Macromolecular Substances - chemistry
Molecular Dynamics Simulation
Quantum Theory
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Summary:We study the role of quantum fluctuations of atomic nuclei in the real-time dynamics of non-equilibrium macro-molecular transitions. To this goal we introduce an extension of the dominant reaction pathways formalism, in which the quantum corrections to the classical overdamped Langevin dynamics are rigorously taken into account to order ℏ 2 . We first illustrate our approach in simple cases, and compare with the results of the instanton theory. Then we apply our method to study the C 7 eq → C 7 ax transition of alanine dipeptide. We find that the inclusion of quantum fluctuations can significantly modify the reaction mechanism for peptides. For example, the energy difference which is overcome along the most probable pathway is reduced by as much as 50%.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.3609244