Quantum mechanical and quasiclassical investigations of the time domain nonadiabatic dynamics of NO2 close to the bottom of the X 2A1 - A 2B2 conical intersection.
We use the effective Hamiltonian that we recently fitted against the first 306 experimentally observed vibronic transitions of NO2 [Joyeux et al., J. Chem. Phys. 119, 5923 (2003)] to investigate the time domain nonadiabatic dynamics of this molecule on the coupled X 2A1 and A 2B2 electronic states, using both quantum mechanical and quasiclassical techniques. From the quantum mechanical point of view, we show that the transfer of population to the electronic ground state originating from a wave packet launched on the excited state occurs in a stepwise fashion. The evolution of wave packets launched on the electronic ground state is instead more complex because the crossing seam is located close to the bottom of the electronic excited state. We next use the mapping formalism, which replaces the discrete electronic degrees of freedom by continuous ones, to obtain a classical description of the coupled electronic states. We propagate Gaussian swarms of trajectories to show that this approach can be used to calculate the populations in each electronic state. We finally propose a very simple trajectory surface hopping model, which assumes that trajectories have a constant probability to jump onto the other state in a particular region of the phase space and a null hopping probability outside from this region. Quasiclassical calculations show that this model enables a precise estimation of complex quantities, as for example the projection of the instantaneous probability density on given planes.
Sanrey
Michaël
M
Laboratoire de Spectrométrie Physique (CNRS UMR5588), Université Joseph Fourier, BP 87, 38402 St. Martin d'Hères, France.
Joyeux
Marc
M