Literature DB >> 25246538

Dynamical traps lead to the slowing down of intramolecular vibrational energy flow.

Paranjothy Manikandan1, Srihari Keshavamurthy2.   

Abstract

The phenomenon of intramolecular vibrational energy redistribution (IVR) is at the heart of chemical reaction dynamics. Statistical rate theories, assuming instantaneous IVR, predict exponential decay of the population with the properties of the transition state essentially determining the mechanism. However, there is growing evidence that IVR competes with the reaction timescales, resulting in deviations from the exponential rate law. Dynamics cannot be ignored in such cases for understanding the reaction mechanisms. Significant insights in this context have come from the state space model of IVR, which predicts power law behavior for the rates with the power law exponent, an effective state space dimensionality, being a measure of the nature and extent of the IVR dynamics. However, whether the effective IVR dimensionality can vary with time and whether the mechanism for the variation is of purely quantum or classical origins are issues that remain unresolved. Such multiple power law scalings can lead to surprising mode specificity in the system, even above the threshold for facile IVR. In this work, choosing the well-studied thiophosgene molecule as an example, we establish the anisotropic and anomalous nature of the quantum IVR dynamics and show that multiple power law scalings do manifest in the system. More importantly, we show that the mechanism of the observed multiple power law scaling has classical origins due to a combination of trapping near resonance junctions in the network of classical nonlinear resonances at short to intermediate times and the influence of weak higher-order resonances at relatively longer times.

Entities:  

Keywords:  Arnold web; Fermi resonance; mode specificity; phase space; wavelets

Year:  2014        PMID: 25246538      PMCID: PMC4209979          DOI: 10.1073/pnas.1406630111

Source DB:  PubMed          Journal:  Proc Natl Acad Sci U S A        ISSN: 0027-8424            Impact factor:   11.205


  27 in total

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Journal:  Science       Date:  2000-09-22       Impact factor: 47.728

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Authors:  M Gruebele; P G Wolynes
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Journal:  Phys Rev Lett       Date:  2012-02-15       Impact factor: 9.161

5.  Slow decay of temporal correlations in quantum systems with Cantor spectra.

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Journal:  Phys Rev Lett       Date:  1992-08-03       Impact factor: 9.161

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Authors:  Edwin L Sibert; Martin Gruebele
Journal:  J Chem Phys       Date:  2006-01-14       Impact factor: 3.488

7.  Theory of mass-independent fractionation of isotopes, phase space accessibility, and a role of isotopic symmetry.

Authors:  Rudolph A Marcus
Journal:  Proc Natl Acad Sci U S A       Date:  2013-06-28       Impact factor: 11.205

8.  Measuring picosecond isomerization kinetics via broadband microwave spectroscopy.

Authors:  Brian C Dian; Gordon G Brown; Kevin O Douglass; Brooks H Pate
Journal:  Science       Date:  2008-05-16       Impact factor: 47.728

9.  Intramolecular vibrational dephasing obeys a power law at intermediate times.

Authors:  M Gruebele
Journal:  Proc Natl Acad Sci U S A       Date:  1998-05-26       Impact factor: 11.205

10.  Theoretical and computational studies of non-RRKM unimolecular dynamics.

Authors:  Upakarasamy Lourderaj; William L Hase
Journal:  J Phys Chem A       Date:  2009-03-19       Impact factor: 2.781

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  3 in total

Review 1.  Locating and Navigating Energy Transport Networks in Proteins.

Authors:  Korey M Reid; David M Leitner
Journal:  Methods Mol Biol       Date:  2021

Review 2.  Molecules and the Eigenstate Thermalization Hypothesis.

Authors:  David M Leitner
Journal:  Entropy (Basel)       Date:  2018-09-05       Impact factor: 2.524

3.  Cavity-Modified Unimolecular Dissociation Reactions via Intramolecular Vibrational Energy Redistribution.

Authors:  Derek S Wang; Tomáš Neuman; Susanne F Yelin; Johannes Flick
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  3 in total

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