Volume 118, 2001

High-resolution IR studies of hydrogen bonded clusters: Large amplitude dynamics in (HCl)n

Abstract

Structural and dynamical information on small hydrogen-bonded systems is revealed by high-resolution IR spectroscopy of HCl dimer, trimer and tetramer. In (HCl)2, four combination bands tentatively assigned to the Van der Waals stretch ν4 and geared band ν5 vibrations are observed. The study focuses on two unexpected results: (i) all of the observed bands are built only on the bound HCl stretch ν2, and (ii) the bands predominantly originate from the 9-fold less populated upper tunneling level of the ground state. Model 3D quantum calculations are presented to show that both these surprising trends originate from the large amplitude tunneling dynamics in the dimer. The (HCl)3 spectra are assigned and analyzed for multiple isotopomeric contributions. The spectral fit reveals large homogeneous line broadening indicating the excited state lifetime of ∽1.6 ns and tentatively associated with dynamics of intramolecular vibrational energy distribution (IVR) induced trimer ring opening. Finally, first high-resolution data on the HCl stretch fundamental spectrum of (HCl)4 are presented.

Article information

Article type
Paper
Submitted
07 Dec 2000
First published
05 Jun 2001

Faraday Discuss., 2001,118, 63-78

High-resolution IR studies of hydrogen bonded clusters: Large amplitude dynamics in (HCl)n

M. Fárník, S. Davis and D. J. Nesbitt, Faraday Discuss., 2001, 118, 63 DOI: 10.1039/B009808F

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