Metastable fragmentation of silver bromide clusters

abundance spectra and the fragmentation channels of silver bromide clusters have been measured and analyzed. The most abundant species are AgnBrn-1+ a nd AgnBrn+1- and Ag14Br13+ is a magic number, revealing their ionic nature. However, some features depart from what is generally observed for alkali-h alide ionic clusters. From a certain size, AgnBrn-1+ is no more the main se ries, and AgnBrn-2,3+ series become almost as important. The fast fragmenta tion induced by a UV laser makes the cations lose more bromine than silver ions and lead to more silver-rich clusters. Negative ions mass spectra cont ain also species with more silver atoms than required by stoichiometry. We have investigated the metastable fragmentation of the cations using a new e xperimental method. The large majority of the cations release mainly a neut ral Ag3Br3 cluster. These decay channels are in full agreement with our rec ent ab initio DFT calculations, which show that Ag+-Ag+ repulsion is reduce d due to a globally attractive interaction of their d orbitals. This effect leads to a particularly stable trimer (AgBr)(3) and to quasi-planar cyclic structures of (AgBr), clusters up to n = 6. We have shown that these two f eatures may be extended to other silver halides, to silver hydroxides (AgOH )(n), and to cuprous halide compounds.