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Article Dans Une Revue Journal of Chemical Physics Année : 2023

Hydrogen - iodine scattering: I. Development of an accurate spin-orbit coupled diabatic potential energy model

Résumé

The scattering of H by I is a prototypical model system for light-heavy scattering in which relativistic coupling effects must be taken into account. Scattering calculations depend strongly on the accuracy of the potential energy surface (PES) model. The methodology to obtain such an accurate PES model suitable for scattering calculations is presented, which includes spin-orbit (SO) coupling within the Effective Relativistic Coupling by Asymptotic Representation (ERCAR) approach. In this approach, the SO coupling is determined only for atomic states of the heavy atom and the geometry dependence of the SO effect is accounted for by a diabatization with respect to asymptotic states. The accuracy of the full model, composed of a Coulomb part and of the SO model, is achieved in the following ways. For the SO model, the extended ERCAR approach is applied, which accounts for both intra-state and inter -state SO coupling and an extended number of diabatic states are included. The corresponding coupling constants for the SO operator are obtained from experiment, which is more accurate than computed values. In the Coulomb Hamiltonian model, special attention is paid to the long range behavior and to accurate c 6 dispersion coefficients. The flexibilty and accuracy of this Coulomb model is achieved by combiningpartial models for three different regions. These are merged via artificial neural networks, which also refine the model further. In this way, an extremely accurate PES model for HI is obtained suitable for accurate scattering calculations.
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dimanche 30 juin 2024
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Dates et versions

hal-04325112 , version 1 (30-12-2023)

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Nicole Weike, Alexandra Viel, Wolfgang Eisfeld. Hydrogen - iodine scattering: I. Development of an accurate spin-orbit coupled diabatic potential energy model. Journal of Chemical Physics, 2023, 159 (24), pp.244119-1-13. ⟨10.1063/5.0186787⟩. ⟨hal-04325112⟩
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