Intramolecular vibrational redistribution: from high-resolution spectra to real-time dynamics

Makarov, A. A.; Malinovsky, A. L.; Ryabov, E. A.

doi:10.3367/ufnr.0182.201210e.1047

Успехи физических наук

2012

DOI: 10.3367/ufnr.0182.201210e.1047

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Intramolecular vibrational redistribution: from high-resolution spectra to real-time dynamics

A. A. Makarov¹,

A. L. Malinovsky²,

E. A. Ryabov³

Abstract: 1 ³ÕÓÑÅÑ ÅÑÄÑÓâ, Ä ÔÑÑÕÄÇÕÔÕÄËË Ô ÐÑÏÇÐÍÎÂÕÖÓÑÌ ØËÏËÚÇÔÍËØ ÄÇÜÇÔÕÄ ì àÕÑ ÃÖÕËÐ-1 Ë ÒÇÐÕËÐ-1 (1-butyne, 1-pentyne), ÅAEÇ ÙË×ÓÂ ÖÍÂÊÞÄÂÇÕ ÐÂ ÒÑÎÑÉÇÐËÇ ÕÓÑÌÐÑÌ ÔÄâÊË C C. £ AEÂÎßÐÇÌÛÇÏ AEÎâ àÕËØ ÏÑÎÇÍÖÎ ÏÞ ÚÂÜÇ ËÔÒÑÎßÊÖÇÏ âÄÐÖá ÔÕÓÖÍÕÖÓÐÖá ×ÑÓÏÖÎÖ, ÐÑ ËÐÑÅAEÂ AEÎâ ÍÓÂÕÍÑÔÕË ì ËØ ÖÒÓÑÜÈÐÐÑÇ ÐÂËÏÇÐÑÄÂÐËÇ.

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Cited by 22 publications

(16 citation statements)

References 260 publications

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“…[3] This result is not surprising because it is well known that IVR times are strongly dependent on excitation energies. [5] We stress again that τ 0 and the IVR time do not coincide, but to some extent these quantities are correlated to each other. The main difference between nitrobenzene and naphthoquinone derivatives is the incident electron energy ε at which we evaluate the anion lifetimes and the corresponding EA a (τ a ) values.…”

mentioning

confidence: 84%

“…[4] τ 0 may also be compared with the typical intramolecular vibrational energy redistribution (IVR) time in high-resolution IR spectroscopy of cooled molecular beams and real-time studies of IVR dynamics, although the IVR time is strongly dependent on energy and molecular structure. [5] It has been shown that the S 2 (1B u + ) excited state of the β-carotene molecule relaxes in 160 fs to S 1 (2A g À ) and then undergoes two distinct stages of IVR, with 200 and 450 fs time constants. [6] The typical timescale in Rice-Ramsperger-Kassel-Markus (RRKM) theory is also about 100 fs.…”

mentioning

confidence: 99%

“…[7] We do not identify the pre-exponential factor τ 0 of Eqn. (1) with the IVR time [5,6] or similar quantities of the statistical theory of mono-molecular reactions. [4,7] In our case, τ 0 is a parameter of a simple Arrhenius model.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Electron affinity evaluation for nitrobenzene derivatives using negative ion lifetime data

Asfandiarov

Pshenichnyuk

Воробьев

et al. 2015

Rapid Comm Mass Spectrometry

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mentioning

confidence: 84%

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confidence: 99%

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Electron affinity evaluation for nitrobenzene derivatives using negative ion lifetime data

Asfandiarov

Pshenichnyuk

Воробьев

et al. 2015

Rapid Comm Mass Spectrometry

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“…The subsequent monomolecular reactions (dissociation, isomerization) are statistical in nature. The fast redistribution of energy from the pumped mode to other vibrations of the molecule (intramolecular vibrational redistribution, IVR (see review articles: [109][110][111][112]) also limits the possibility of selective vibrational multiphoton excitation of the selected modes of polyatomic molecules above the randomization threshold. Research on intramolecular relaxation, i.e.…”

mentioning

confidence: 99%

STRUCTURAL DYNAMICS OF FREE MOLECULES AND CONDENSED STATE OF MATTER. Part II. TRANSIENT STRUCTURES IN CHEMICAL REACTIONS

2017

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Basic knowledge of mankind so far relates to the description of electrons and atoms in the material in a state of equilibrium, where the behavior changes slowly over time. The electron diffraction with a high temporal and space resolution has opened the possibility of direct observation of the processes occurring in the transient state of the substance (molecular movie). Here it is necessary to provide a temporary resolution of the order of 100 fs, which corresponds to the transition of the system through the energy barrier of the potential surface, which describes the chemical reaction - the process of the breaking and the formation of new bonds between the interacting agents. Thus, the possibility of the investigation of the coherent nuclear dynamics of molecular systems and the condensed matter can be opened. In the past two decades, it has been possible to observe the nuclear motion in the temporal interval corresponding to the period of the nuclear oscillation. The observed coherent changes in the nuclear system at such temporal intervals determine the fundamental shift from the standard kinetics of chemical reactions to the dynamics of the phase trajectory of a single molecule, the molecular quantum state tomography.

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“…In this continuing quest a fundamental and formidable phenomenon that needs to be reckoned with is that of intramolecular vibrational energy redistribution (IVR) (1)(2)(3)(4)(5). Although models of reaction rates like the Rice-Ramsperger-Kassel-Marcus (RRKM) theory and transition state theory (TST) continue to be of immense value in terms of their conceptual elegance and ease of application, the deviations from these paradigms due to incomplete IVR can lead to a deeper understanding of reaction dynamics and control (6,7).…”

mentioning

confidence: 99%

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

Paranjothy

Keshavamurthy

2014

Proc. Natl. Acad. Sci. U.S.A.

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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.phase space | wavelets | Arnold web | Fermi resonance | mode specificity U nderstanding, quantifying, and manipulating chemical reactions have been holy grails of chemical physics for nearly a century. In this continuing quest a fundamental and formidable phenomenon that needs to be reckoned with is that of intramolecular vibrational energy redistribution (IVR) (1-5). Although models of reaction rates like the Rice-Ramsperger-Kassel-Marcus (RRKM) theory and transition state theory (TST) continue to be of immense value in terms of their conceptual elegance and ease of application, the deviations from these paradigms due to incomplete IVR can lead to a deeper understanding of reaction dynamics and control (6, 7). Recent studies in both gas (8, 9) and condensed phases (10, 11) indicate that a detailed knowledge of the mechanism of IVR is a prerequisite for formulating dynamically consistent rate theories and, possibly, novel control strategies. Despite the challenges that arise due to the sheer complexity and richness of the IVR process (1), significant advances have been made over the past couple of decades, using a combination of innovative experimental techniques (12, 13) and novel theoretical approaches (14, 15).The present work focuses on one such novel theoretical approach, based on an analogy between IVR and the phenomenon of Anderson localization, proposed in the seminal work of Logan ...

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Intramolecular vibrational redistribution: from high-resolution spectra to real-time dynamics

Cited by 22 publications

References 260 publications

Electron affinity evaluation for nitrobenzene derivatives using negative ion lifetime data

Electron affinity evaluation for nitrobenzene derivatives using negative ion lifetime data

STRUCTURAL DYNAMICS OF FREE MOLECULES AND CONDENSED STATE OF MATTER. Part II. TRANSIENT STRUCTURES IN CHEMICAL REACTIONS

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

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