Clusters of the transition metals were generated by laser vaporisation of a sample of the metal into the throat of a pulsed supersonic expansion. This allowed clusters with internal temperatures as low as 5 K to be routinely prepared. Mass-selective detection was accomplished by multi-photon ionisation of the clusters within the ion source of a time - of - flight mass spectrometer. Use of a tunable laser to carry out electronic excitation, prior to ionisation, allowed mass - resolved resonant two - photon ionisation spectra of the clusters to be recorded. Real time control of the experiment and automated data logging was achieved using software developed to run on an IBM PC - AT microcomputer. This allowed multiple ion signals to be recorded simultaneously whilst carrying out R2PI or time-resolved studies on the metal cluster species in the beam. Resonant two - photon ionisation spectroscopic studies were carried out on the ( 0 - 0 ) and ( 1 - 0 ) bands of the J X system of Cu9 and the A X system of Ag->. The 0.04 cm-1 bandwidth of the tunable dye laser used allowed rotationally resolved spectra to be recorded. The spectra recorded for these systems showed them both to be AA = 0 ( or AS2 = 0 ) transitions. The J state of CU2 was assigned to the 1 Zj state derived from the ?P + atomic limit at Dg(X) + 45821 cm-1. Rotational analysis of the spectra yieldedl | lthe following constants for the Cu2 isotopomer: Bg = 0.1166(1) cm , ae = 0.0021(1) cm-1. This gave Rg = 2.138(1) A for the J state, shorter than the ground state bond length. Accordingly the transition was assigned to 3ditg -*?4piru, to give the above assignment. The rotational constants obtained, for the *?7Ag-, isotopomer, from analysisI _ | *of the spectra of the A X system of Ag-, were: Bg = 0.0447(3) cm , ae= 0.0004(2) cm'*, and Bq = 0.0490(18) cm"1. These gave bond lengths of Rg = 2.649(9) A and Rq = 2.530(46) A. The observed Ail = 0 transition agreed with the previous assignment of the A state as 0* arising from the 5sag -+ 5sau promotion.