Phase-shift studies of ligand exchanges between tert-butyl alcohol and amines in excited mercury complexes in the gas phase

Abstract

The Hg(6³P₁) photosensitized luminescence of tert-butyl alcohol (AL)–amine (AM) mixtures has been investigated by a phase-shift method. For AL–AM mixtures, the lifetime of an HgAL* complex evaluated from the phase delays, between the mercury 253.7 nm fluorescence and the 300 nm luminescence arising from the HgAL* complex, decreased at high pressures with increasing amine pressure, while the lifetime of an HgAM* complex did not change upon addition of AL. From the dependence of amine pressure on the HgAL* lifetime, the rate constants for ligand-exchange reactions have been determined. The rate constants obtained by the phase-shift method are in good agreement with those estimated from the effect of amines on the emission intensity from the HgAL* complex.