The Problem of Molecular States in the Framework of the Standard Adiabatic Approach

It is shown that nonzero asymptotic nonadiabatic couplings of molecular states are a fundamental property of the standard Born–Oppenheimer approach to studying inelastic processes in collisions of atoms and/or ions. The given connections provide the correct boundary conditions for radial nuclear wave functions. It is also shown that failure to take into account nonzero asymptotic relations leads to physical artifacts. The solution to these problems is achieved by applying the reprojection method, which considers nuclear dynamics in the asymptotic regions before and after the collision in the representation of scattering channels and in the interaction region in the representation of molecular states.