H + H2 reaction barrier: A fixed-node quantum Monte Carlo study

Publisher Website
Google Scholar
Abstract
The classical barrier height for the H+H2 exchange reaction, as well as the energies at two other points along the reaction path, are calculated using fixed‐node quantum Monte Carlo (FNQMC). Several single‐determinant importance functions are used at the saddle point in order to relate the quality of the importance function to the accuracy and precision of the final result. The computed barrier is an upper bound since the energy of H and of H2 is obtained exactly by FNQMC. Our best upper bound (9.70±0.13 kcal/mol) has a mean within 0.1 kcal/mol of the presumed exact value. This best bound is obtained with a single determinant, double‐zeta basis importance function. Contrary to experience with expansion methods, it is found that an importance function with a basis set of near Hartree–Fock quality, as well as one derived from a spin‐unrestricted SCF calculation, are among the least efficient and least accurate of the importance functions used. Specifically, a nodal surface appearing in the lowest energy molecular orbital in these functions apparently increases the FNQMC energy. The FNQMC energy at the two other points along the reaction path is found to agree with the most accurate CI results of Liu to within statistical error.