A free-jet infrared double resonance study of the threshold region of IVR. The ν6, ν1 + ν6, and 2ν1 bands of propyne

Go, J.; Cronin, Thomas J.; Perry, David S.

doi:10.1016/0301-0104(93)80233-y

Cited by 66 publications

(27 citation statements)

References 42 publications

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“…Experiments by Lehmann, Scoles, and coworkers [92] indicate that the overtone state 3ν 1 has a faster IVR rate as compared to the nearly degenerate ν 1 + 2ν 6 combination state. Similarly Go, Cronin, and Perry in their study [124] found evidence for a larger number of perturbers for the 2ν 1 state than for the ν 1 + ν 6 state. The spectrum corresponding to both the first and the second overtone states implied a lack of direct low-order Fermi resonances.…”

Section: Quantum Mechanism: Vibrational Superexchangementioning

confidence: 99%

Dynamical tunnelling in molecules: quantum routes to energy flow

Keshavamurthy¹

2007

International Reviews in Physical Chemistry

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Dynamical tunneling, introduced in the molecular context, is more than two decades old and refers to phenomena that are classically forbidden but allowed by quantum mechanics. The barriers for dynamical tunneling, however, can arise in the momentum or more generally in the full phase space of the system. On the other hand the phenomenon of intramolecular vibrational energy redistribution (IVR) has occupied a central place in the field of chemical physics for a much longer period of time. Despite significant progress in understanding IVR a priori prediction of the pathways and rates is still a difficult task. Although the two phenomena seem to be unrelated several studies indicate that dynamical tunneling, in terms of its mechanism and timescales, can have important implications for IVR. It is natural to associate dynamical tunneling with a purely quantum mechanism of IVR. Examples include the observation of local mode doublets, clustering of rotational energy levels, and extremely narrow vibrational features in high resolution molecular spectra. Many researchers have demonstrated the usefulness of a phase space perspective towards understanding the mechanism of IVR. Interestingly dynamical tunneling is also strongly influenced by the nature of the underlying classical phase space. Recent studies show that chaos and nonlinear resonances in the phase space can enhance or suppress dynamical tunneling by many orders of magnitude. Is it then possible that both the classical and quantum mechanisms of IVR, and the potential competition between them, can be understood within the phase space perspective? This review focuses on addressing the question by providing the current state of understanding of dynamical tunneling from the phase space perspective and the consequences for intramolecular vibrational energy flow in polyatomic molecules.

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Section: Quantum Mechanism: Vibrational Superexchangementioning

confidence: 99%

Dynamical tunnelling in molecules: quantum routes to energy flow

Keshavamurthy¹

2007

International Reviews in Physical Chemistry

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“…±ÑàÕÑÏÖ ÄÓÂÜÂÕÇÎßÐÂâ ÔÕÓÖÍÕÖÓÂ ÒÑÎÑÔÞ ÑÚÇÐß ÃÎËÊÍÂ ÔÕÓÖÍÕÖÓÇ ÒÂÓÂÎÎÇÎßÐÑÌ ÒÑÎÑÔÞ ÔËÏÏÇÕÓËÚÐÑÅÑ ÄÑÎÚÍÂ Ô ÒÓÂÄËÎÂÏË ÒÂÕß ÅÓÂÐËÙÖ ÒÇÓÇØÑAEÂ ÍÑÎÇÃÂÕÇÎßÐÑÅÑ AEÄËÉÇÐËâ ÑÕ ÓÇÅÖÎâÓÐÑÅÑ Í ÔÕÑØÂÔÕËÚÇÔÍÑÏÖ. ±ÇÓÄÂâ ÒÑÒÞÕÍÂ ÃÞÎÂ ÒÓÇAEÒÓËÐâÕÂ Ä ÓÂÃÑÕÂØ [190,191], ÅAEÇ ÑÔÖÜÇÔÕÄÎâÎÂÔß ÔÒÇÍÕÓÑÔÍÑÒËâ ÔÑÔÕÑâÐËâ j2n 1 i ÏÑÎÇÍÖÎÞ ÒÓÑÒËÐÂ HC CCH 3 Ô ËÔÒÑÎßÊÑÄÂÐËÇÏ AEÄÖØÔÕÖÒÇÐÚÂÕÑÅÑ ª¬-ÄÑÊÃÖÉAEÇÐËâ Ë ËÊÏÇÓÇÐËâ ÒÑÅÎÑÜÇÐËâ ÐÂ ÒÇÓÇØÑAEÇ jn 1 i 3 j2n 1 i. ¹ÖÕß ÒÑÊAEÐÇÇ ÃÞÎË ÒÓÑÄÇAEÇÐÞ àÍÔÒÇÓËÏÇÐÕÞ Ô ÒÓâ-ÏÞÏ ÄÑÊÃÖÉAEÇÐËÇÏ ÒÇÓÇØÑAEÂ j0i 3 j2n 1 i Ë ÑÒÕÑÕÇÓÏËÚÇ-ÔÍËÏ AEÇÕÇÍÕËÓÑÄÂÐËÇÏ [192].´ÂÍ ÍÂÍ ÔÍÑÎßÍÑ-ÐËÃÖAEß ÔÇÓßÈÊÐÞØ ÐÂÏÇÍÑÄ ÐÂ IVR ËÊ ÔÑÔÕÑâÐËâ j2n 1 i ÐÇ ÐÂÃÎá-AEÂÎÑÔß, ÃÞÎ ËÔÔÎÇAEÑÄÂÐ ÄÕÑÓÑÌ ÑÃÇÓÕÑÐ.…”

Section: ¤Aeç ë íâí óâôôïñõóçððþç àîçïçðõþ õçñóëëunclassified

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

Makarov¹,

Malinovsky²,

Ryabov³

2012

Успехи физических наук

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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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“…In particular, the study of 3ν 1 and 3ν 1 + ν 3 revealed that weak anharmonic perturbations affect the K structure of these states (13). The bands 2ν 1 (5,14) and 3ν 1 (15) were also studied at sub-Doppler resolution, evidencing line fractionation due to coupling of the bright state to the dense vibrational bath. Gambogi et al (14) showed that for the K = 0 clumps of the 3ν 1 band, the fractionation increases with 2J + 1, but the full width at half maximum (FWHM), of the order of 0.04 cm −1 , for the K = 0 clumps was largely independent of J .…”

Section: Introductionmentioning

confidence: 97%

“…Propyne and to a very small extent its isotopomers have been the subject of numerous overtone studies (5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16). The photographic infrared spectrum of the 3ν 1 band of propyne was obtained by Herzberg et al (6) already in the 1930's.…”

Section: Introductionmentioning

confidence: 99%