Vibrational relaxation of OH (X 2Πi, v=2)

Abstract

Vibrational relaxation rates for the v=2 level of the X 2Πi state of the OH radical have been measured in a low pressure flow system, using a novel two-laser pump-and-probe technique. The OH is prepared in the v=2 level by overtone pumping (2←0) and monitored by ultraviolet laser-induced fluorescence in the (1,2) band of the A–X system. Scanning the time delay between the lasers at a given collider pressure produces exponential decay whose rate as a function of collider pressure yields the rate constant. We determine values (all cm3 s−1 units) for NH3: (1.20±0.15)×10−10; CH4: (2.3±0.2)×10−12; CO2: (6.7±1.1)×10−13; N2O: (4.6±0.6)×10−13; O2: (2.6±0.54)×10−13; N2 and H2: ≤10−14. Except for ammonia, these are two to three orders of magnitude smaller than those measured for relaxation of v=1 in the A 2Σ+ excited state of OH, where attractive forces appear to play a role.