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Copper carbonyl cations of the form Cu(CO)(n)(+) (n = 1-8) are produced in a molecular beam via laser vaporization in a pulsed nozzle source. Mass-selected infrared photodissociation spectroscopy in the carbonyl stretching region is used to study these ions and their argon "tagged" analogues. The geometries and electronic states of these complexes are determined by the number of infrared-active bands, their frequency positions, and their relative intensities compared to the predictions of theory. Cu(CO)(4)(+) has a completed coordination sphere, consistent with its expected 18-electron stability. It also has a tetrahedral structure similar to that of its neutral isoelectronic analog Ni(CO)(4). The carbonyl stretch in Cu(CO)(4)(+) (2198 cm(-1)) is blue-shifted with respect to the free CO vibration (2143 cm(-1)), providing evidence that this is a "non-classical" metal carbonyl.

Gas-phase metal carbonyl cations of the vanadium-group metals (V(+), Nb(+), Ta(+)) were produced in a molecular beam by laser vaporization and then mass-analyzed and size-selected in a time-of-flight spectrometer and studied with IR laser photodissociation spectroscopy in the carbonyl-stretching region. The abundances in the mass spectra, the fragmentation patterns, and the IR spectra provided a combined approach that revealed the coordination numbers in these systems. Although seven-coordinate structures would have 18 electrons in each case, V(CO)(6)(+) was found to be formed rather than V(CO)(7)(+). Nb(+) formed both six- and seven-coordinate species, while Ta(+) formed only the Ta(CO)(7)(+) complex. Density functional theory computations were used to predict the IR spectra for these systems, which are dramatically different for the six- and seven-coordinate structures and in excellent agreement with the measurements. V(CO)(6)(+) and Nb(CO)(6)(+) have structures slightly distorted from octahedral, while Nb(CO)(7)(+) and Ta(CO)(7)(+) have C(3v) capped octahedral structures.

Chromium oxide cluster cations, Cr(n)O(m)+, are produced by laser vaporization in a pulsed nozzle cluster source and detected with time-of-flight mass spectrometry. The mass spectrum exhibits a limited number of stoichiometries for each value of n, where m > n. The cluster cations are mass selected and photodissociated using the second (532 nm) or third (355 nm) harmonic output of a Nd:YAG laser. At either wavelength, multiphoton absorption is required to dissociate these clusters, which is consistent with their expected strong bonding. Cluster dissociation occurs via elimination of molecular oxygen, or by fission processes producing stable cation species and/or eliminating stable neutrals such as CrO3, Cr(2)O(5), or Cr(4)O(10). Specific cation clusters identified to be stable because they are produced repeatedly in the decomposition of larger clusters include Cr(2)O(4)+, Cr(3)O(6)+, Cr(3)O(7)+, Cr(4)O(9)+, and Cr(4)O(10)+.

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