Reaction path Hamiltonian: Tunneling effects in the unimolecular isomerization HNC→HCN

S. K. Gray, W. H. Miller, Y. Yamaguchi, H. F. Schaefer
1980 Journal of Chemical Physics  
The reaction path Hamiltonian model recently formulated by Miller, Handy, and Adams [J, Chern. Phys. 99 (1980)] is applied to the uni~ molecular isomerization HNC + HCN. The reaction path, and the energy and force constant matrix along it, are calculated at the SCF level with a large basis set ("double zeta plus polarization"), and the micro~ canonical rate constant k(E) is computed in the energy range near and below the classical threshold of the reaction, It is seen, for example, 5 ~l that
more » ... ample, 5 ~l that rates as fast as 10 sec can occur at energies -8 kcal/mole below the classical threshold.
doi:10.1063/1.440494 fatcat:py5npp3pprfndbcmsbn6t262xm