Ultrafast, correlated multidimensional shell dynamics of neon matrices after photoexcitation of an NO impurity: An MCTDH approach

Photoexcitation of NO embedded in rare gas matrices triggers a shock-wave like radial perturbation of the surrounding rare gas atoms. In this Letter, we present quantum dynamical studies of this process, based on a radial shell model. The high-dimensional quantum dynamics is preformed with the multi-configuration time dependent Hartree (MCTDH) method. By comparison with time-dependent Hartree (TDH) results, we study the effects of dynamical correlations. Their inclusion modifies the high-dimensional wavefunction, however, mean values are well described within the TDH ansatz. Finally, pump–probe signals are simulated and shown to lead to small but measurable effects when including the correlations.