Transfer and quenching rate constants for XeF(B) and XeF(C) state in low vibrational levels

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Abstract
The relative XeF(B–X) and XeF(C–A) emission intensities from the steady‐state vacuum ultraviolet photolysis of XeF2 have been used to measure the B–C transfer and quenching rate constants of XeF molecules in low vibrational levels. The rare gases N2, CF4, SF6, F2, NF3, CF3H, CF3Cl, HF, CO2, and XeF2 were investigated as buffer gases at room temperature. The transfer rate constants are much larger than the quenching rate constants for He, Ne, Ar, Kr, N2, CF4, and SF6. For Xe, NF3, CHF3, and CClF3 transfer is only 2–4 times faster than quenching and for F2, HF, and CO2 quenching is faster than B–C state transfer. Quenching for XeF(D) was studied for rare gases and for N2. No convincing evidence was found for three‐body quenching by the rare gases and their quenching of the XeF(B, C) and XeF(D) states are reported as two‐body processes for pressures below ∼5 atm. The XeF(D) quenching rate constants are of the same magnitude as the B–C state transfer rate constants. The photochemical and collisional (metastable rare gas atom) dissociative excitation of XeF2 and KrF2 are summarized in the Appendix.