Intramolecular vibrational energy redistribution and the quantum ergodicity transition: a phase space perspective

The onset of facile intramolecular vibrational energy flow can be related to features in the connected network of anharmonic resonances in the classical phase space.

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Intramolecular vibrational energy redistribution in DCO (X̃2A′): Classical-quantum correspondence, dynamical assignments of highly excited states, and phase space transport

Physical Chemistry Chemical Physics ◽

10.1039/b308813h ◽

2003 ◽

Vol 5 (22) ◽

pp. 5051-5062 ◽

Cited By ~ 50

Author(s):

Aravindan Semparithi ◽

Srihari Keshavamurthy

Keyword(s):

Phase Space ◽

Excited States ◽

Vibrational Energy ◽

Energy Redistribution ◽

Intramolecular Vibrational Energy Redistribution ◽

Phase Space Transport ◽

Classical Quantum ◽

Quantum Correspondence

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Intramolecular vibrational energy redistribution in HCCCH2X (X = Cl, Br, I) measured by femtosecond pump–probe experiments in a hollow waveguide

Physical Chemistry Chemical Physics ◽

10.1039/c7cp08561c ◽

2018 ◽

Vol 20 (16) ◽

pp. 10949-10959 ◽

Cited By ~ 5

Author(s):

Alexander Kushnarenko ◽

Eduard Miloglyadov ◽

Martin Quack ◽

Georg Seyfang

Keyword(s):

Energy Flow ◽

Vibrational Energy ◽

Strong Dependence ◽

Hollow Waveguide ◽

Energy Redistribution ◽

Time Resolved ◽

Pump Probe ◽

Intramolecular Vibrational Energy Redistribution ◽

Initial Excitation ◽

Bichromophoric Molecules

Time resolved femtosecond probing of intramolecular energy flow after excitation of the two different infrared CH-chromophores in these bichromophoric molecules shows strong dependence on the chemical environment of the initial excitation.

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Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions

Communications Chemistry ◽

10.1038/s42004-019-0252-y ◽

2020 ◽

Vol 3 (1) ◽

Cited By ~ 1

Author(s):

Sourav Karmakar ◽

Pankaj Kumar Yadav ◽

Srihari Keshavamurthy

Keyword(s):

Phase Space ◽

Statistical Models ◽

Energy Flow ◽

Vibrational Energy ◽

Reaction Rates ◽

High Dimensional ◽

Intramolecular Dynamics ◽

Delayed Onset ◽

The Stability ◽

Classical Phase Space

AbstractStatistical models provide a powerful and useful class of approximations for calculating reaction rates by bypassing the need for detailed, and often difficult, dynamical considerations. Such approaches invariably invoke specific assumptions about the extent of intramolecular vibrational energy flow in the system. However, the nature of the transition to the statistical regime as a function of the molecular parameters is far from being completely understood. Here, we use tools from nonlinear dynamics to study the transition to statisticality in a model unimolecular reaction by explicitly visualizing the high dimensional classical phase space. We identify generic features in the phase space involving the intersection of two or more independent anharmonic resonances and show that the presence of correlated, but chaotic, intramolecular dynamics near such junctions leads to nonstatisticality. Interestingly, akin to the stability of asteroids in the Solar System, molecules can stay protected from dissociation at the junctions for several picoseconds due to the phenomenon of stable chaos.

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