Intramolecular energy transfer between oriented chromophores: High-resolution infrared spectroscopy of HCl trimer

Abstract

Detailed dynamical and structural information has been obtained for hydrogen-bonded (HCl)(3) clusters via high-resolution IR laser absorption spectroscopy in a supersonic slit expansion. Multiple rovibrational bands in an approximately 3000 cm(-1) HCl stretch region have been assigned and analyzed for H (35)Cl/H (37)Cl isotopomeric contributions, corresponding to excitation of (i) the degenerate antisymmetric HCl stretch in isotopically pure (H (35)Cl)(3), (ii) high- and low-frequency components of the nearly degenerate HCl stretch in H (37)Cl (H (35)Cl)(2), (iii) the low-frequency component of the corresponding HCl stretch in (H (37)Cl)(2) H (35)Cl. The isotopically pure (H (35)Cl)(3) results are in good agreement with earlier diode-laser efforts. A simple exciton model for vibrational coupling between HCl subunits is presented that indicates rapid intramolecular energy flow (beta approximately -1.89 cm(-1), tau approximately 2.8 ps) in the trimer ring, which is in good agreement with vibrationally mediated tunneling rates observed in the HCl dimer. Spectral analysis at slit jet resolution indicates a Deltanu approximately 120 MHz homogeneous line broadening and an excited-state lifetime of approximately 1.3 ns. The data is consistent with intramolecular vibrational redistribution-induced opening of the trimer followed by true predissociation to either (HCl)(2)+HCl or 3HCl on a longer time scale.