Construction of a Mode-Combination Hamiltonian under the Grid-Based Representation for the Quantum Dynamics of OH + HO2 → O2 + H2O

In this work, a systematic construction framework on a mode-combination Hamiltonian operator of a typical polyatomic reaction, OH + HO₂ → O₂ + H₂O, is developed. First, a set of Jacobi coordinates are employed to construct the kinetic energy operator (KEO) through the polyspherical approach ( Phys. Rep. 2009, 484, 169). Second, due to the multiconfigurational electronic structure of this system, a non-adiabatic potential energy surface (PES) is constructed where the first singlet and triplet states are involved with spin–orbital coupling. To improve the training database, the training set of random energy data was optimized through a popular iterative optimization approach with extensive trajectories. Here, we propose an automatic trajectory method, instead of the classical trajectory on a crude PES, where the gradients are directly computed by the present ab initio calculations. Third, on the basis of the training set, the potential function is directly constructed in the canonical polyadic decomposition (CPD) form ( J. Chem. Theory Comput. 2021, 17, 2702−2713) which is helpful in propagating the nuclear wave function under the grid-based representation. To do this, the Gaussian process regression (GPR) approach for building the CPD form, called the CPD-GPR method ( J. Phys. Chem. Lett. 2022, 13, 11128−11135) is adopted where we further revise CPD-GPR by introducing the mode-combination (mc) scheme leading to the present CPD-mc-GPR approach. Constructing the full-dimension non-adiabatic Hamiltonian operator with mode combination, as test calculations, the nuclear wave function is propagated to preliminarily compute the reactive probability of OH + HO₂ → O₂ + H₂O where the reactants are prepared in vibrational ground states and in the first triplet electronic state.