Slow periodic oscillations in time domain dynamics of NO2

The authors investigated the time domain nonadiabatic dynamics of NO2 on the coupled X 2A1 and A 2B2 electronic states by launching wave packets on the excited electronic state and focused on the evolution at long times (t>200 fs), which has received little attention up to now. The authors showed that the initial fast spreading of the wave packets is followed at all energies by slow periodic intramolecular vibronic energy redistribution (IVER) with periods in the range of 0.3 to several tens of picoseconds. These energy transfers lead to oscillations with the same periods in the population of each electronic state. Propagation of wave packets indicates that IVER frequencies also dominate the fluctuations of the squared modulus of the autocorrelation function |A(t)|2 at energies not too high above the bottom of the conical intersection, but this is no longer the case at higher energies. For example, for initial wave packets prepared by almost vertical excitation of the vibrational ground state of the ground electronic surface, the oscillations of |A(t)|2 essentially reflect the detuning from 1:2 resonance between the frequency of the bend and that of the symmetric stretch in the excited electronic state. These theoretical results were used to discuss the possible origin of the low-frequency oscillations which were recently observed in time domain experimental spectra of NO2.