Quantum mechanical and quasiclassical investigations of the time domain nonadiabatic dynamics of NO2 close to the bottom of the XA12‐AB22 conical intersection

摘要: We use the effective Hamiltonian that we recently fitted against first 306 experimentally observed vibronic transitions of NO2 [Joyeux et al., J. Chem. Phys. 119, 5923 (2003)] to investigate time domain nonadiabatic dynamics this molecule on coupled XA12 and AB22 electronic states, using both quantum mechanical quasiclassical techniques. From point view, show transfer population ground state originating from a wave packet launched excited occurs in stepwise fashion. The evolution packets is instead more complex because crossing seam located close bottom state. next mapping formalism, which replaces discrete degrees freedom by continuous ones, obtain classical description states. propagate Gaussian swarms trajectories approach can be used calc...