Supersonic copper clusters

Abstract

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.