Spectroscopic analysis of transition state energy levels: Bending–rotational spectrum and lifetime analysis of H3 quasibound states

We report converged quantum mechanical calculations of scattering matrices and transition probabilities for the reaction of H with H2 with total angular momentum 0, 1, and 4 as functions of total energy in the range 0.85–1.15 eV on an accurate potential energy surface. These calculations show energy dependences that may be attributed to dynamical resonances with vibrational quantum numbers (100 0) and (111 0). The resonance structure is illustrated with Argand diagrams, and we present state-to-state reactive collision delay times and lifetimes. For J=0, 1, and 4, we found the lowest-energy H3 resonance at total energies of 0.983, 0.985, and 1.01 eV, respectively, with lifetimes of about 16–17 fs. For J=1 and 4 there is a higher-energy resonance at 1.10–1.11 eV; for J=1 the lifetime is about 4 fs and for J=4 it is about 1 fs.