Tackling Non-Adiabatic Effects by Time-Dependent Density Functional Theory

摘要

A quantitative theory of excited-state lifetimes, non-radiative transitions, and many photochemical reactions requires knowledge of non-adiabatic couplings between Born-Oppenheimer states. Efficient methods to compute non-adiabatic couplings for molecules with 100 and more atoms from first principles are almost exclusively based on time-dependent density functional methods [1] and have become available only very recently. I will summarize a time-dependent response theory approach [2] which builds on analytical excited state gradient methods. Benchmarks show an insignificant increase in total computation times if the non-adiabatic couplings are evaluated during an excited state gradient calculation. I will present an efficient non-adiabatic molecular dynamics method based on these techniques which uses Gaussian basis functions and does not require explicit propagation of the electronic wavefunction. Applications will include excited state non-radiative lifetimes and photo-induced electrocyclic reactions.