Non-adiabatic excited-state time-dependent GW molecular dynamics (TDGW) satisfying extended Koopmans’ theorem: An accurate description of methane photolysis

Abstract

There is a longstanding difficulty that time-dependent density functional theory relying on adiabatic local density approximation is not applicable to the electron dynamics, for example, for an initially excited state, such as in photochemical reactions. To overcome this, we develop non-adiabatic excited-state time-dependent GW molecular dynamics (TDGW) on the basis of the extended quasiparticle theory. Replacing Kohn–Sham orbitals/energies with correlated, interacting quasiparticle orbitals/energies allows the full correspondence to the excited-state surfaces and corresponding total energies, with satisfying extended Koopmans’ theorem. We demonstrate the power of TDGW using methane photolysis, CH4→CH3•+H, an important initiation reaction for combustion/pyrolysis and hydrogen production of methane. We successfully explore several possible pathways and show how this reaction dynamics is captured accurately through simultaneously time-tracing all quasiparticle levels. TDGW scales as O(NB3-4), where NB is the number of basis functions, which is distinctly advantageous to performing dynamics using configuration interaction and coupled cluster methods.