Abstract
This work reports non-radiative internal conversion (IC) rate constants obtained for Cun with n = 3, 6,and 9 andH2 onCu3. TheTime-Dependent Density Functional Theory (TDDFT) methodwas employedwith three different functionals in order to investigate the electronic structures and the absorptionspectra. The performance of the generalized gradient approximation of Perdew, Burke and Ernzerhof(PBE) and the hybrid B3LYP and PBE0 exchange correlation functionals in combination with the SVPand the def2-TZVP basis setswas examined.TDDFTresults were used as input data to compute internalconversion rate constants. For this purpose, we have developed a program package. A descriptionof the theoretical background used in our numerical implementation and the program input file ispresented. In viewof future applications of this program package in photoinduced catalysis, we presentthe analysis of the IC rate processes for the photodissociation of H2 on Cu3. These results showedthe applicability of the method and the computational program to identify the vibrational modes intransition metal clusters giving rise to the largest IC rate constant due to their interactions with theexcited electronic states occurring in the hot-electron induced dissociation phenomena.