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Abstract:
Based on quantum reactive-scattering theory, we propose a method for studying the electronic nonadiabaticity in collision processes involving electron-ion rearrangements. We investigate the state-to-state transition probability for electron-ion rearrangements with two comparable approaches. In the first approach the information of the electron is only contained in the ground-state Born-Oppenheimer potential-energy surface, which is the starting point of common reactive-scattering calculations. In the second approach, the electron is explicitly taken into account and included in the calculations at the same level as the ions. Hence, the deviation in the results between the two approaches directly reflects the electronic nonadiabaticity during the collision process. To illustrate the method, we apply it to the well-known proton-transfer model of Shin and Metiu, generalized in order to allow for reactive scattering channels. We show that our explicit electron approach is able to capture electronic nonadiabaticity and the renormalization of the reaction barrier near the classical turning points of the potential in nuclear configuration space. In contrast, system properties near the equilibrium geometry of the asymptotic scattering channels are hardly affected by electronic nonadiabatic effects. We also present an analytical expression for the transition amplitude of the asymmetric proton-transfer model based on the direct evaluation of integrals over the involved Airy functions.
