X3Σg- → b1Σg+ Absorption Spectra of Molecular Oxygen in Liquid Organic Solvents at Atmospheric Pressure.

Spectra and absorption coefficients of the forbidden 765 nm X3Σg- → b1Σg+ transition of molecular oxygen dissolved in organic solvents at atmospheric pressure were recorded over a 5 m path length using a liquid waveguide capillary cell. The results show that it is possible to investigate this weak near-infrared absorption transition in a common liquid hydrocarbon solvent without the need for a potentially dangerous high oxygen pressure. Proof-of-principle data from benzene, toluene, chlorobenzene, bromobenzene, and iodobenzene reveal a pronounced heavy atom effect on this spin-forbidden transition. For example, the absorption coefficient at the band maximum in iodobenzene, (28.9 ± 3.3) × 10-3 M-1 cm-1, is approximately 21 times larger than that in benzene, (1.4 ± 0.1) × 10-3 M-1 cm-1. These absorption measurements corroborate results obtained from O2(X3Σg-) → O2(b1Σg+) excitation spectra of O2(a1Δg) → O2(X3Σg-) phosphorescence, which depended on data from a plethora of convoluted experiments. Spectroscopic studies of molecular oxygen in liquid solvents can help evaluate aspects of the seminal Strickler-Berg approach to treat the effect of solvent on Einstein's A and B coefficients for radiative transitions. In particular, our present results are a key step toward using the O2(X3Σg-) → O2(b1Σg+) transition to evaluate the speculated limiting condition of applying the Strickler-Berg treatment to a highly forbidden process. This latter issue is but one example of how an arguably simple homonuclear diatomic molecule continues to aid the scientific community by providing fundamental physical insight.