화학공학소재연구정보센터
Journal of Chemical Physics, Vol.113, No.8, 3055-3066, 2000
Dynamics of the vibrational predissociation of HCl dimer
A comprehensive study of the vibrational predissociation dynamics of the HCl dimer is reported. The predissociation lifetimes for three H-Cl stretch vibrationally excited states of ((HCl)-Cl-35)(2) have been measured. Companion measurements for the (HCl)-Cl-35 . (HCl)-Cl-37 complex have also been made. These lifetimes range from 16(2) to 46(5) ns, lifetimes that are more than 10(6) times longer than the H-Cl stretch vibrational period. The correlated HCl(v' = 0,j(')) + HCl(v' = 0,j(')) fragment rotational state distributions have also been determined. These show a predominant dynamical bias that favors the production of j',j " pairs that maximize the rotational energy of the fragments and minimize their translational energy. The j',j " distribution is well described by a simple energy gap model of the dissociation. The results suggest a complex, for which there are substantial excursions from the equilibrium geometry, dissociation from a wide range of geometries, weak coupling of the H-Cl stretch vibrations to the dissociation coordinate, and a blurring of the distinction between hydrogen bonded and free HCl moieties. These results are consistent with theoretical studies of the HCl dimer potential energy surface.