Flash spectroscopy with mercury resonance radiation. Part 5.—Formation and relaxation of Hg(63P0)

Abstract
Relaxation rates of Hg(63P0) were investigated following black-body flash excitation and also following monochromatic flash excitation with the 2537 Å resonance line. In an excess of N2 with black-body excitation, the Hg(63P0) exhibited anomalously slow decay profiles which were attributed to the production of N2A3∑+ u by energy transfer from highly excited states of mercury. Accurate deactivation rates of Hg(63P0) by H2, NO, CO, O2, CO2, N2O, CH4, C2H6, C3H8, C2H4 and NH3 were measured by monitoring the weak 2537 Å afterglow following monochromatic excitation with very low flash energies. Quantum yields for the Hg(63P1 → 0) relaxation were also measured in each of the gases, by comparing the [Hg(63P0)] with that formed in N2 with the same fractional quenching of Hg(63P1). The nature and symmetry of the intermediate complexes in Hg-photosensitised reactions were formulated with qualitative molecular orbital considerations. It was suggested that the relative stability of Hg(63P0) with respect to collisional deactivation is generally due simply to the decreased internal energy.

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