Rate constants for collision-induced emission of O(aΔ) with He, Ne, Ar, Kr, N, CO and SF as collisional partners.

Rate constants for singlet oxygen collision induced emission of the a1Δg-X3Σ-g transition at 1.27 μm were measured for CO2, N2, SF6, and rare gases as collisional partners. Photolysis of ozone by 266 nm laser radiation produced singlet oxygen. We performed direct measurements of pressure dependences of the 1.27 μm emission intensity for partner gases. The measured rate constants kMa-X in the units of 10-24 cm3 s-1 are as follows: CO2 - 10 ± 2; N2 - 3.2 ± 0.6; SF6 - 7 ± 1; He - 1.1 ± 0.3; Ne - 1.3 ± 0.3; Ar - 2.8 ± 0.6; Kr - 6 ± 1. The measured values of kMa-X are close to the values calculated from absorption measurements. Considering the known rate constants kMb-a for the b1Σg+-a1Δg transition in the gas phase we found that the ratio kMa-X/kMb-a was constant and independent of a collisional partner according to the "spin-orbit based" mechanism of intensity borrowing proposed by Minaev (THEOCHEM, 1989, 183, 207). However, this ratio amounted to (1.3 ± 0.2) × 10-4, which is considerably lower than the theoretically predicted value of (3-6) × 10-4.