Abstract

We report a combined experimental and computational study of the structure and fragmentation dynamics of mixed ligand gas-phase ion-molecule complexes. Specifically, we have studied the infrared spectroscopy and vibrationally induced photofragmentation dynamics of mass-selected Au(CO)x(N2O)y+ complexes. The structures can be understood on the basis of local CO and N2O chromophores in different solvation shells with CO found preferentially in the core. Rich fragmentation dynamics are observed as a function of complex composition and the vibrational mode excited. The dynamics are characterized in terms of branching ratios for different ligand loss channels in light of calculated internal energy distributions. Intramolecular vibrational redistribution appears to be rapid, and dissociation is observed into all energetically accessible channels with little or no evidence for preferential breaking of the weakest intermolecular interactions.

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