Journal of Chemical Physics, Vol.106, No.8, 3078-3089, 1997
High-Resolution Midinfrared Spectroscopy of Arh2O - The V(2) Bend Region of H2O
Six internal rotation/vibration bands of ArH2O are observed in a slit supersonic expansion via direct absorption of a tunable diode laser in the upsilon(2) bend region of H2O. The spectra obtained for the ortho H2O manifold are well represented by a pseudodiatomic model with nearly free internal rotation of the H2O subunit. By way of contrast, the para bands show significant mixing between the internal rotor and stretch states, indicative of strong angular-radial coupling in the intermolecular potential. The spectra for the para Ar-H2O species can be deperturbed based on a three state Coriolis plus angular-radial coupling model which includes microwave, far-ir and near-ir data. The results indicate a redshift of approximate to 0.58 cm(-1) upon bend excitation of the H2O subunit, and in general rather modest changes in the excited state intermolecular potential from the ground state potential. No indication of predissociation broadening is found, and the instrument-limited linewidths place a lower limit on the vibrational lifetime in the excited state of tau greater than or equal to 7.2(6) ns.
Keywords:POTENTIAL-ENERGY SURFACE;WEAKLY-BOUND COMPLEX;LASER SPECTROSCOPY;VANDERWAALS BONDS;AR-H2O;ROTATION;VIBRATION;DYNAMICS;PREDISSOCIATION;STABILIZATION