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Extremely slow intramolecular vibrational redistribution: Direct observation by time-resolved raman spectroscopy in trifluoropropyne

  • Atoms, Spectra, Radiations
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Abstract

We have studied the dynamics of intramolecular vibrational redistribution (IVR) from the initially excited mode v1 ≈ 3330 cm−1 (acetylene-type H-C bond) in H-C≡C-CF3 molecules in the gaseous phase by means of anti-Stokes spontaneous Raman scattering. The time constant of this process is estimated as 2.3 ns—this is the slowest IVR time reported so far for the room-temperature gases. It is suggested that so long IVR time with respect to the other propyne derivatives can be explained by a larger defect, in this case, of the Fermi resonance of v1 with v2 + 2v7—the most probable doorway state leading to IVR from v1 to the bath of all vibrational-rotational states with the close energies. In addition, it is shown that the observed dynamics is in agreement with a theoretical model assuming strong vibrational-rotational mixing.

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Authors and Affiliations

  1. Institute of Spectroscopy, Russian Academy of Sciences, Troitsk, Moscow region, 142190, Russia

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

  2. Moscow Institute of Physics and Technology, Dolgoprudnyi, Moscow region, 141700, Russia

    A. A. Makarov

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  1. A. L. Malinovsky
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  2. A. A. Makarov
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  3. E. A. Ryabov
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Correspondence to A. A. Makarov.

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Malinovsky, A.L., Makarov, A.A. & Ryabov, E.A. Extremely slow intramolecular vibrational redistribution: Direct observation by time-resolved raman spectroscopy in trifluoropropyne. Jetp Lett. 93, 124–128 (2011). https://doi.org/10.1134/S0021364011030106

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