No abstract

Reactions on the surface of a variety of transition metal clusters have been studied in the gas phase at near room temperature using a newly developed fast-flow reaction device. Initial examples of the use of this device are provided by survey studies of the reactivity of iron, cobalt, nickel, copper, and niobium clusters in contact with low concentrations of D2, N2 and CO. Dissociative chemisorption of D2 is found to occur with dramatic sensitivity to cluster size in the cases of iron, cobalt, and niobium clusters, the detailed pattern of reactivity differing markedly for each metal. The corresponding reaction is also observed with nickel clusters, but here the reactivity shows only a slow, steady increase with cluster size. Copper clusters are found to be completely unreactive to H2 chemisorption under these conditions. Molecular nitrogen is found to chemisorb readily to clusters of cobalt and niobium, with a reactivity pattern very similar to that observed with D2. Iron clusters are found to show slight reactivity with N2; only a small amount of chemisorption is observed on the most reactive clusters at high N2 concentration, but the pattern of this reactivity with cluster size is consistent with that observed in D2 chemisorption. In contrast to these highly structured reactivity patterns of D2 and N2, carbon monoxide is found to show only a slow, monotonic increase in reactivity with cluster size. It is suggested that these dramatic reactivity patterns for chemisorption on metal clusters provide stringent tests for future theories as to the nature of chemisorption on metal surfaces at a detailed, molecular level.

SiC2 has been prepared in a supersonic molecular beam by laser vaporization of a silicon carbide rod within a pulsed supersonic nozzle. Rotational analysis of the 0-0 band of the well-known 4980 Å band system of this molecule reveals that, contrary to previous assumptions, the molecule is triangular in both the ground and excited electronic states. In both states the molecule is of C2V symmetry with a C–Si–C angle between 40° and 41°. The correct assignment of the spectrum is Ã ′B2←x̃ ′A1. The carbon–carbon bond length is 1.25 Å in the ground state, suggesting that the molecule is best understood as a silicon atom bound to the side of a triply bonded C2 fragment. The optical transition moment is polarized along the b axis of the molecule which is parallel to the carbon–carbon bond axis. In the Ã 1B2 excited state the carbon–carbon bond opens up to 1.30 Å consistent with a π*←π excitation of the carbon–carbon triple bond. The silicon–cargon distance is measured to be 1.81 Å in the x̃ 1A1 state, lengthening to 1.88 Å in the Ã ′B2 excited state. In addition, the ionization potential of SiC2 was determined to lie between 8.91 and 10.38 eV.

Copper clusters ranging in size from 1 to 29 atoms have been prepared in a supersonic beam by laser vaporization of a rotating copper target rod within the throat of a pulsed supersonic nozzle using helium for the carrier gas. The clusters were cooled extensively in the supersonic expansion [T(translational) 1 to 4 K, T(rotational)=4 K, T(vibrational)=20 to 70 K]. These clusters were detected in the supersonic beam by laser photoionization with time-of-flight mass analysis. Using a number of fixed frequency outputs of an exciplex laser, the threshold behavior of the photoionization cross section was monitored as a function of cluster size. The 7.9 eV photon energy of the F2 excimer laser was found to be above the ionization potential of all clusters, and the photoion mass spectrum thus produced showed the copper cluster concentration in the beam to follow a monotonically decreasing function of cluster size. The 6.4 eV ArF exciplex laser photon energy was found to be above the photoionization threshold of clusters with three or more atoms in the case of odd-numbered clusters, but only for clusters with eight or more atoms for even-numbered clusters. Extending out to clusters as large as 29 atoms, laser photoionization at 6.4 eV produced a time-of-flight mass distribution with a pronounced even/odd alternation in cluster photoion intensity. This alternation in ionization threshold behavior was attributed to an even/odd alternation in the electronic structure of the copper clusters with the highest occupied molecular orbital (HOMO) of the even clusters being considerably more strongly bonding than it is in the clusters with an odd number of copper atoms. The 4.98 eV photon energy of the KrF exciplex laser was found to lie below the ionization threshold of all clusters in the 1 to 29 atom range. An extensive survey of the ultraviolet absorption spectrum of the copper dimer was also performed with this supersonic beam source. Resonance two-photon ionization (R2PI) with mass selective detection allowed the detection of five new electronic band systems in the region between 2690 and 3200 Å, for each of the three naturally occurring isotopic forms of Cu2. In the process of scanning the R2PI spectrum of these new electronic states, the ionization potential of the copper dimer was determined to be 7.894±0.015 eV.

A new fast flow device for the study of metal cluster reactions in the gas phase is described and characterized. The new device utilizes metal clusters made by laser vaporization of an appropriate metal target mounted in the throat of a supersonic nozzle which exhausts into a fast-flow reaction tube. Reactants are injected into the flowing helium–metal cluster mixture at a point in the flow tube where shock waves have reheated the gas to roughly 320 K. Turbulence in the wake of these shock waves produces efficient mixing of the reactants. Measurement of the flow properties of this reaction tube indicate a residence time of 150–200 μs with an average density of helium buffer gas equivalent to 50–100 Torr at room temperature. Subsequent free expansion of this reaction mixture into a large vacuum chamber produces a supersonic beam with extensive cooling of the various constituents in the mixture (pyrazine was measured to be rotationally cooled to 10 K). The new cluster reaction device is, therefore, an excellent source for future studies of the jet-cooled metal cluster reaction products themselves.