Quantum mechanical treatment of stationary and dynamical properties of bound vibrational systems. Application to the relaxation dynamics of Ag5 after an electron photodetachment

An ab initio quantum mechanical approach for the calculation of stationary and dynamical properties of vibrational systems with up to 30 non-separable degrees of freedom is presented. The method is based on a representation of the Watson Hamiltonian in spaces spanned by harmonic-oscillator eigenfunctions. The applicability of the scheme is demonstrated by an investigation of the short-time vibrational relaxation following the photodetachment of one electron of a cold Ag5− cluster. A pronounced energy flow into a particular vibrational mode is observed on a picosecond time scale. This indicates that a control of the nuclear motion, for instance by laser pulses, should in principle be possible for systems with a relatively large number of degrees of freedom.