TRAJECTORY SURFACE HOPPING STUDY OF THE LI-2(X-1-SIGMA(+)(G)) DISSOCIATION REACTION(LI)

Trajectory surface hopping calculations are reported for the Li + Li-2 (X(1)Sigma(g)(+)) dissociation reaction over the range of translationa l energies 13 less than or equal to E-tr/kcal mol(-1) less than or equ al to 80. Both potential energy surfaces for ground doublet Li-3, whic h have been modeled from the double many-body expansion method (DMBE I II), have been employed in the dynamics calculations. For the initial internal state (upsilon = 0, j = 10), the behavior of the dissociative cross sections as a function of translational energy shows that nonad iabatic effects are important over the whole range of energies studied . Concerning the role of initial vibration, it has been found that, fo r E-tr = 25 kcal mol(-1) and j = 10, the adiabatic dissociative cross sections are enhanced as upsilon increases from 0 to 20, while the non adiabatic ones just slightly increase with the vibrational quantum num ber.