The reaction of Hg(6 3P1) with hydrogen molecules studied by electron spin resonance and laser induced fluorescence

Abstract

Mercury atoms were excited to the 6 3P1 state with a pulsed laser and a lamp at 253.7 nm in the presence of H2, D2, HD, and mixtures of these gases. The hydrogen atom reaction products were detected by vacuum ultraviolet (VUV) laser induced fluorescence. The ratio of yields of the two body channel (mercury hydride and a hydrogen atom) and the three body channel [Hg(6 1S0) and two hydrogen atoms] were determined by combining the H/D atom ratios and a literature value of the HgD/HgH ratio from reaction with HD. Assuming that the sum of the two yields is unity, the yield of the two body channel is for H2 0.63±0.15, for D2 0.79±0.11, and for HD 0.10±0.02 (HgH+D) and 0.65±0.03 (HgD+H). The average kinetic energies calculated by combining these yields with the literature data on internal energy release in the mercury hydride molecules agree with the average kinetic energies measured from the Doppler broadened fluorescence excitation curves. When the E vector of the exciting polarized light was rotated there was no effect on the hydrogen atom spectrum proving that the hydrogen atom velocity distribution is isotropic. When the mercury atoms were excited with circularly polarized light to the J=1, MJ=1 state, the hydrogen atoms exhibited no spin polarization. Electron spin resonance (ESR) signals observed when irradiating a mixture of Hg and hydrogen molecules were shown by isotopic effects to be due to hydrogen atoms dissociated from mercury hydride molecules.