Quantum mechanical treatment of stationary and dynamical properties of bound vibrational systems. Application to the relaxation dynamics of Ag 5 after an electron photodetachment

Abstract

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 Ag 5 − 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.