Full-Dimensional Potential Energy Surface for RO-Vibrationally Inelastic Scattering Between H < Inf > 2 < / Inf > Molecules
Journal of Chemical Theory and Computation
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We report a new full-dimensional potential energy surface (PES) for the inelastic scattering between ro-vibrationally excited H2 molecules. The new PES is based on 39,462 multi-reference configuration interaction points in dynamically relevant regions. The analytic form of the PES consists of a short-range term fit with the permutational invariant polynomial-neural network method and a long-range term with a physically correct asymptotic functional form accounting for both electrostatic and dispersion terms, which are connected smoothly with a switching function. The PES compares favorably with existing accurate PESs near the H2 equilibrium geometries but covers a much larger configuration space for H2 with up to 10 vibrational quanta. Full-dimensional quantum scattering calculations on the new PES reproduce the recent Stark-induced adiabatic Raman passage results for the HD(v = 1) + H2 scattering near 1 K, validating its accuracy. These calculations also revealed significant differences with existing PESs in describing scattering of vibrationally excited molecules, underscoring the ability of the new PES in handling such dynamics.
Potential energy surfaces
Atomic, Molecular and Optical Physics | Power and Energy
Full-Dimensional Potential Energy Surface for RO-Vibrationally Inelastic Scattering Between H < Inf > 2 < / Inf > Molecules.
Journal of Chemical Theory and Computation, 17(11),