QUANTUM-MECHANICAL TREATMENT OF STATIONARY AND DYNAMICAL PROPERTIES OF BOUND VIBRATIONAL SYSTEMS - APPLICATION TO THE RELAXATION DYNAMICS OF AG-5 AFTER AN ELECTRON PHOTODETACHMENT

An ab initio quantum mechanical approach for the calculation of statio nary and dynamical properties of vibrational systems with up to 30 non -separable degrees of freedom is presented. The method is based on a r epresentation of the Watson Hamiltonian in spaces spanned by harmonic- oscillator eigenfunctions. The applicability of the scheme is demonstr ated by an investigation of the short-time vibrational relaxation foll owing 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 nucl ear motion, for instance by laser pulses, should in principle be possi ble for systems with a relatively large number of degrees of freedom. (C) 1997 Published by Elsevier Science B.V.