Frequency map analysis of the 3D vibrational dynamics of the LiCN/LiNC molecular system

Losada, Juan Carlos; Benito, R. M.; Borondo, F.

doi:10.1140/epjst/e2008-00862-0

Cited by 11 publications

(10 citation statements)

References 34 publications

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“…The Hamiltonian can now be specified using the Born-Oppenheimer potential energy surface 21 and the usual approximations 9,13 as…”

Section: A Non-driven Isomerization Of Licnmentioning

confidence: 99%

“…Its use in resolving rates in chemical reactions has been demonstrated in several systems including the isomerization reaction of lithium cyanide (LiNC/LiCN). The latter has received a lot of attention [8][9][10][11][12][13][14][15][16][17][18][19][20] in part because of the early introduction of a useful model potential by Essers et al 21 Recently, for example, some of us 20 obtained the decay rate of trajectories near the normally hyperbolic invariant manifold (NHIM) for this reaction so as to demonstrate the use of nonrecrossing dividing surfaces in time-dependent transition state theory (TST). 22 In turn, the objective of this paper is to demonstrate a stronger connection between rates obtained using MFPT to those from flux-over-population formulas.…”

Section: Introductionmentioning

confidence: 99%

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Mean first-passage times for solvated LiCN isomerization at intermediate to high temperatures

Schleeh,

Reiff,

García-Müller

et al. 2022

Preprint

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The behavior of a particle in a solvent has been framed using stochastic dynamics since the early theory of Kramers. A particle in a chemical reaction reacts slower in a diluted solvent because of the lack of energy transfer via collisions. The flux-over-population reaction rate constant rises with increasing density before falling again for very dense solvents. This Kramers turnover is observed in this paper at intermediate and high temperatures in the backward reaction of the LiNC LiCN isomerization via Langevin dynamics and mean first-passage times (MFPTs). It is in good agreement with the Pollak-Grabert-Hänggi (PGH) reaction rates at lower temperatures. Furthermore, we find a square root behavior of the reaction rate at high temperatures and have made direct comparisons of the methods in the intermediate-and high-temperature regimes; all suggesting increased ranges in accuracy of both the PGH and MFPT approaches.

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“…The Hamiltonian can now be specified using the Born-Oppenheimer potential energy surface 21 and the usual approximations 9,13 as…”

Section: A Non-driven Isomerization Of Licnmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Mean first-passage times for solvated LiCN isomerization at intermediate to high temperatures

Schleeh,

Reiff,

García-Müller

et al. 2022

Preprint

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“…That is, the time evolution of the SALI gives a clear indication of those periods of time in which a (globally) ergodic trajectory is (locally) influenced by the regular or almost regular structures that exists in the mixed phase space of this molecular system [47,48].…”

Section: Local Behavior Of a Global Ergodic Trajectory Influenced By mentioning

confidence: 99%

Using the small alignment index chaos indicator to characterize the vibrational dynamics of a molecular system: LiNC-LiCN

et al. 2015

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A study of the dynamical characteristics of the phase space corresponding to the vibrations of the LiNC-LiCN molecule using an analysis based on the small alignment index (SALI) is presented. SALI is a good indicator of chaos that can easily determine whether a given trajectory is regular or chaotic regardless of the dimensionality of the system, and can also provide a wealth of dynamical information when conveniently implemented. In two-dimensional (2D) systems SALI maps are computed as 2D phase space representations, where the SALI asymptotic values are represented in color scale. We show here how these maps provide full information on the dynamical phase space structure of the LiNC-LiCN system, even quantifying numerically the volume of the different zones of chaos and regularity as a function of the molecule excitation energy.

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“…Interestingly, although the central issues involved in IVR and long time celestial dynamics have a certain mathematical similarity, the LFA approach has been utilized much more in the context of celestial mechanics when compared to molecular systems. Borondo and coworkers have utilized this approach to gain insights into intramolecular dynamics of several systems [164,165], especially the LiCN ↔ LiNC isomerization reaction. Without offering any reasons for this imbalance, and rather than getting into a discussion on the relative merits and demerits of the various approaches, we turn our attention to the wavelet-based LFA.…”

Section: Time-frequency Analysismentioning

confidence: 99%

Scaling Perspective on Intramolecular Vibrational Energy Flow: Analogies, Insights, and Challenges

Keshavamurthy¹

2013

Advances in Chemical Physics

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Frequency map analysis of the 3D vibrational dynamics of the LiCN/LiNC molecular system

Cited by 11 publications

References 34 publications

Mean first-passage times for solvated LiCN isomerization at intermediate to high temperatures

Mean first-passage times for solvated LiCN isomerization at intermediate to high temperatures

Using the small alignment index chaos indicator to characterize the vibrational dynamics of a molecular system: LiNC-LiCN

Scaling Perspective on Intramolecular Vibrational Energy Flow: Analogies, Insights, and Challenges

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