Journal of Chemical Physics, Vol.119, No.15, 7824-7837, 2003
The dissociation adiabaticity parameter and the strong field dissociation of H-2(+)
Walsh have proposed a dissociation adiabaticity parameter, gamma(Dv)equivalent to(D-v/2U(pm))(1/2), where D-v is the dissociation energy from vibrational state v and U-pm is the molecular ion system's ponderomotive energy [T. D. G. Walsh, L. Strach, and S. L. Chin, J. Phys. B 31, 4853 (1998)]. We modify this parameter and assess its utility in the interpretation of kinetic energy distributions of the atoms and protons that are produced by quantum wave-packet simulations of the H-2(+) dissociation process. This modified parameter, gamma(mol), is found to be a useful indicator of when a dissociation process can be best described using multiphoton processes involving field dressed electronic states (gamma(mol)>1) or when it can be better described in the quasistatic approximation as barrier suppressed dissociation (gamma(mol)<1). Field dressed electronic states and oscillating potential energy curve tails govern the behavior at the extreme values of gamma(mol), i.e., gamma(mol)>1 or <1, respectively. (C) 2003 American Institute of Physics.