Clusters of atoms/molecules show dynamics characteristic of the method of excitation. Two contrasted processes are discussed: (1) electronic excitation via single-photon absorption and (2) impulsive excitation of nuclear motions by surface impact. Process 1 is exemplified by photodissociation dynamics of size-selected metal cluster ions. The electronic energy is converted most likely to vibrational energy of internal modes; dissociation follows via statistical mechanism to produce energetically favored fragments. Exceptionally, a silver cluster ion, Ag4+, is shown to undergo nonstatistical dissociation along the potential-energy surface of the excited state. Energy partitioning to translational and vibrational modes of fragments is analyzed as well as bond dissociation energies. Furthermore, the spectrum of the photodissociation yield provides electronic and geometrical structures of a cluster with the aid of ab initio calculations; manganese, MnN +, and chromium, CrN+, cluster ions are discussed, where the importance of magnetic interactions is manifested. On the other hand, momentum transfer upon surface impact plays a role in process 2. An impulsive mechanical force triggers extraordinary chemical processes distinct from those initiated by atomic collision as well as photoexcitation. Experiments on aluminum, AlN-, silicon, SiN-, and solvated, I2-(CO2)N, cluster anions provide evidence for reactions proceeding under extremely high temperatures, such as pickup of surface atoms, annealing of products, and mechanical splitting of chemical bonds. In addition, a model experiment to visualize and time-resolve the cluster impact process is performed by using a micrometer-sized liquid droplet. Multiphoton absorption initiates superheating of the droplet surface followed by a shock wave and disintegration into a number of small fragments (shattering). These studies further reveal how the nature of chemical bonds influences the dynamics of clusters.
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