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Statistical intramolecular vibrational relaxation and its hindrance: The fundamentals of (CH3)3C–C≡CH and (CH3)3Si–C≡CH (1990)

Lehmann, K. K. ; Pate, B. H. ; Scoles, G.

College Park, Md. : American Institute of Physics (AIP)

The Journal of Chemical Physics 93 (1990), S. 2152-2153

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ISSN: 1089-7690

Source: AIP Digital Archive

Topics: Physics , Chemistry and Pharmacology

Notes: We have measured the fundamental acetylenic C–H stretch near 3.0 μm of (CH3)3C–C≡CH and (CH3)3Si–C≡CH using an optothermal, molecular beam spectrometer. We find that the individual R(J) lines of the hydrocarbon are Lorentzian with a FWHM of 800 MHz indicating statistical intramolecular vibrational relaxation (IVR) with a 400 ps lifetime. The R(J) lines of the silicon compound are clearly asymmetric and, in addition, show a FWHM of about 150 MHz indicating a much longer (〉2 ns) lifetime. The increase in IVR lifetime in the larger density of states molecule may be due to reduced kinetic coupling resulting from the heavier Si atom.

Type of Medium: Electronic Resource

URL: http://dx.doi.org/10.1063/1.459042

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