Spectra and time-dependent dynamics of H3 near the conical intersection in the (2p)1E′ ground electronic manifold

Abstract

We report on the spectra and dynamics of H3 near the conical intersection in its (2p)1E′ ground electronic manifold. The time-dependent wave packet approach and the double many-body expansion (DMBE) potential energy surface (PES) are employed for this purpose. We use Jacobi coordinates (R,r,γ) and employ the fast Fourier transform method for R and r, and the discrete variable representation method for γ, in conjunction with the split-operator formalism to describe the evolution of the wave packet (WP) in space and time, respectively. While the main focus of the present work is to explicitly reveal the effects of nonadiabatic coupling between the two sheets of the DMBE PES, companion calculations are also carried out to investigate the dynamics on the uncoupled upper and lower adiabatic sheets, both in two and three dimensions (for total angular momentum J=0). A set of pseudospectra is calculated by Fourier transforming the time autocorrelation function of suitably chosen Gaussian wave packets located initially at the minimum energy point of the seam of conical intersections. The eigenstates thus obtained are assigned by computing their eigenfunctions by spectral quantization. In the coupled states treatment the WP is propagated in the diabatic representation. The time dependence of the adiabatic populations is calculated by using suitable adiabatic projection operators. We find strong effects of nonadiabatic coupling on the discrete vibrational energy levels of the upper adiabatic sheet, which all change to quasibound states in the coupled manifold. The comparison of the decay dynamics of various levels of the upper adiabatic sheet indicates considerable mode specificity (their lifetimes typically vary between 3 and 6 fs). On the other hand, resonances are seen to be less pronounced near the conical intersection on the lower adiabatic sheet (when compared to those in the literature, obtained near the collinear saddle point region). The effect of nonadiabatic coupling on them is only minor. We also report preliminary results on the optical emission spectrum of H3 and compare them with the experimental findings.