Larsen R Wugt, Hegelund F, Nelander B
Chemical Center, Department of Chemical Physics, Lund University, P.O. Box 124, S-22100 Lund, Sweden.
Phys Chem Chem Phys. 2005 May 7;7(9):1953-9. doi: 10.1039/b416924g.
The high-resolution far-infrared absorption spectrum of the intermolecular HC1 libration band upsilon6(1) (upsilonB) of the gaseous molecular complex H12CN-HCl and the two isotopically substituted species H13CN-HCl and D12CN-HCl is recorded by means of static gas-phase Fourier transform far-infrared spectroscopy at 205 K using an electron storage ring source. The rotational structure of the upsilon6(1) band has the typical appearance of a perpendicular type band of a linear polyatomic molecule. The structure is analyzed using a standard semi-rigid linear molecule model including l-type doubling to yield the band origin upsilon0, together with values for the upper state rotational constant B', the upper state quartic centrifugal distortion constant D'j and the value for the l-type doubling constant q6. The values for the ground-state spectroscopic constants B" and D"j for D12CN-H35Cl and H13CN-H35Cl are determined for the first time by ground state combination difference analyses. A number of upsilon6(1) + upsilon7(1) - upsilon7(1) and upsilon6(1) + 2upsilon7(2) - 2upsilon7(2) hot bands are observed in the spectra and the sum of the anharmonicity constants X(6,7) + g(6,7) is estimated. The observed decrease of the rotational constant B together with the simultaneous increase of the quartic centrifugal distortion constant Dj upon excitation of the HCl libration mode indicate that the hydrogen bond in the molecular complex is significantly destabilized upon intermolecular vibrational excitation. The calculated harmonic force constants for the intermolecular hydrogen bond stretching vibration upsilon(sigma) for the ground state and the excited HCl libration state indicate that the excitation of the HCl libration mode destabilizes the intermolecular interaction between HCN and HCl by almost 20%. The hydrogen bond is elongated by 0.030 A upon excitation of the upsilon6(1) mode.
