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Title: Molecular beam laser spectroscopy of the molecules Cu2, CuAg and Ag2
Author: James, Andrew Moray
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1990
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Transition metal clusters were generated by laser vaporisation in the throat of a pulsed supersonic expansion. Detection was accomplished by pulsed laser photoionisation in the source of a time-of-flight mass spectrometer (University of Edinburgh), or by laser-induced fluorescence (LIF) using a ring dye laser (National Research Council of Canada, Ottawa). A variety of metal cluster systems from the first and second transition periods were probed using laser photoionisation time-of-flight mass spec-trometry. Resonant two photon ionisation (R2PI) spectroscopy was performed on the A «— X system of CuAg, and the A state conclusively demonstrated tp have 0"*" symmetry. Rotational analysis yielded T"C =2.3664(71) X and re =2.508(14) X for 63Cu107 Ag. The collision-free lifetime for the v = 0 level of the A state was determined to be 32 ± 2 ns. Congested ultraviolet band systems lying at twice the A «— X transition energy were probed using vibronic R2PI spectroscopy. Ring dye laser fluorescence spectroscopy was used to probe the A «— X system of Ag2 with Doppler-limited resolution. A rotational analysis gave re =2.53118(28) X and r'e =2.65337(31) X. The adiabatic ionisation potentials of Cu2 and CuAg were determined using threshold ionisation spectroscopy (TIS) to be 7.90426(42) eV and 7.78058(54) eV respectively. The dissociation energies of the ion ground states were accordingly determined to be 1.83(08) eV (Cu2) and 1.56(10) eV (CuAg). Rich autoionisation structure in the post-threshold region was observed for both these systems. Electronic excitation in the Group Ib transition metal dimers is discussed in the light of the R2PI, LIF and TTS results.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available