First ultraviolet absorption band of methane: An ab initio study

Abstract

Quantum mechanical calculations of the cross sections for photodissociation of CH4 and CD4 in the 1t2-->3s band are presented. The potential energy surfaces for the three states correlating with the 1 1T2 state at tetrahedral geometries are calculated. The elements of the (3x3) matrix representing the electronic Hamiltonian in the diabatic basis are expanded in powers of nuclear coordinates, up to the second order. The expansion coefficients are based on accurate multireference configuration interaction calculations. The electronically nonadiabatic dynamics is treated with the multiconfiguration time-dependent Hartree approach. All nine internal degrees of methane are included in the quantum dynamics simulations. The calculated cross section agrees well with experiment. Semiclassical calculations using the reflection principle suggest that the peaks in the spectrum correspond to the three adiabatic electronic states correlating with the 1 1T2 state at Td geometries. However, the non-Born-Oppenheimer terms in the Hamiltonian have a strong effect on the positions of the peaks in the absorption spectrum. The results of semiclassical calculations, which neglect these terms, are therefore quite different from the accurate quantum results and experiment.