Spin–Orbit Relaxation of Hg(63P1) by Various Gases

The spin–orbit relaxation of Hg(63P1) to yield Hg(63P0) was investigated in the presence of various gases. The quantum yields of Hg(63P0) formation (defined as relaxation to Hg(63P0)/total relaxation) in the presence of CO, CO2, NH3, ND3, H2O, D2O, C2H6, c-C3H6, C(CH3)4, C3H8, 2,2-C3H6D2, C3D8, n-C4H10 and i-C4H10 were: 0.88 ± 0.07, <0.01, 1.05 ± 0.05, 1.00 ± 0.08, 0.76 ± 0.18, 1.06 ± 0.26, 0.64 ± 0.16, 0.56 ± 0.10, 0.58 ± 0.02, 0.14 ± 0.01, 0.51 ± 0.07, 0.47 ± 0.10, 0.11 ± 0.01, and 0.05 ± 0.01, respectively. The extent of the spin–orbit relaxation process appears to be related in an inverse manner to the availability and accessibility of channels leading to the formation of Hg(61S0), rather than to the fulfillment of electronic–vibrational resonance conditions. This in turn suggests the existence of Hg(63P1)—quencher intermediates having lifetimes long enough to permit several vibrations.