Variation of the Intersection Point of the Potential Surface Crossing Induced by the Laser Phase Along the Reaction Path in Ion-Molecule Reactions: Application To Li+ + CH4

Abstract

A laser ion-molecule reaction interaction through both polarizability and dipole moment contribution leads to variation in the intersection point in potential energy surface crossings along the reaction path; the polarizability is maximum and the dipole changes its sign at s = 4 a.u., defining a virtual transition state. Using the gauge representation (electric field gauge) for a wave length λ = 20.6 μm, intensity I = 5×1012 W/cm2, I = 1×1013 W/cm2, I = 3×1013 W/cm2, we show here that we can create a laser-induced potential energy surface crossing along the reaction path (s = 7-8 a.u.). We illustrate such effects for the Li H + CH 3 + ↔ Li+ + CH4 reaction which takes the form of inverted Morse (without a barrier) using ab initio methods for calculating the reaction path and electric properties of the ion-molecule reaction.