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ABSTRACT The natural reaction coordinates (NRC) are not well suitable for the dynamical investigation of the transfer of the light atom in chemical exchange reactions. In this case the curvature of the reaction coordinate is large and the... more
ABSTRACT The natural reaction coordinates (NRC) are not well suitable for the dynamical investigation of the transfer of the light atom in chemical exchange reactions. In this case the curvature of the reaction coordinate is large and the probability flux gets across the region of multi-valuedness of the NRC. We introduce a new coordinate system (the matching coordinates, MC), that are specially adapted for the reactions with large curvature, and suggest a new method for solving equations of motion in those coordinates. The multi-valuedness is eliminated by drawing a cut from the centre of maximum curvature of the reaction coordinate curve. Matching of the wavefunction and its normal derivative is performed along the cut. The matching conditions play the role of the operator that is responsible for the direct interaction between the reactant and product regions of a potential energy surface and promotes nonadiabatic transitions between them. The matrix Schrödinger equation for the translational motion is converted into a form that can be solved by the previously elaborated effective procedure. The construction of the scattering matrix for this problem, involving equations of motion with constraints (the matching conditions), needs a special projection technique.