Theory of mode specific vibrational predissociation: The HF dimer

Abstract

Quantum mechanical close coupling calculations on (HF)2 vibrational predissociation are presented. The model considers vibrational excitation of the proton donor monomer. The other momomer is frozen at its equilibrium position. The linewidth (lifetime) and final state rotational distribution of the initially vibrationally excited HF were calculated using the artificial channel method. The potential surface was taken from Cournoyer and Jorgensen. The calculated linewidth is in good agreement with recent experimental measurements. This result is drastically different from what is obtained in the collinear model, merely reflecting the important influence of the rotational–vibrational coupling in the highly anisotropic systems. The final rotational distribution of the initially excited HF monomer is highly inverted. The possibility of a rotational in conjunction with a conventional vibrational HF laser is raised.