Self-reaction of hydroxyl radicals, OH + OH → H(2)O + O (1a) and OH + OH → H(2)O(2) (1b), was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 298-834 K temperature and 1-100 bar pressure ranges (bath gas He). A heatable high-pressure flow reactor was employed. Hydroxyl radicals were prepared using reaction of electronically excited oxygen atoms, O((1)D), produced in photolysis of N(2)O at 193 nm, with H(2)O. The temporal behavior of OH radicals was monitored via transient absorption of light from a dc discharge in H(2)O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The results of this study combined with the literature data indicate that the rate constant of reaction 1a, associated with the pressure independent component, decreases with temperature within the temperature range 298-414 K and increases above 555 K. The pressure dependent rate constant for (1b) was parametrized using the Troe expression as k(1b,inf) = (2.4 ± 0.6) × 10(-11)(T/300)(-0.5) cm(3) molecule(-1) s(-1), k(1b,0) = [He] (9.0 ± 2.2) × 10(-31)(T/300)(-3.5±0.5) cm(3) molecule(-1) s(-1), F(c) = 0.37.

Reaction of methyl radicals with hydroxyl radicals, CH(3) + OH → products (1) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 294-714 K temperature and 1-100 bar pressure ranges (bath gas He). Methyl radicals were produced by photolysis of acetone at 193.3 nm. Hydroxyl radicals were generated in reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N(2)O at 193.3 nm, with H(2)O. Temporal profiles of CH(3) were recorded via absorption at 216.4 nm using xenon arc lamp and a spectrograph; OH radicals were monitored via transient absorption of light from a dc discharge H(2)O/Ar low pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light inside the reactor was determined by an accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The results of this study indicate that the rate constant of reaction 1 is pressure independent within the studied pressure and temperature ranges and has slight negative temperature dependence, k(1) = (1.20 ± 0.20) × 10(-10)(T/300)(-0.49) cm(3) molecule(-1) s(-1).

2-Nitrophenol is an important component of "brown carbon" in the atmosphere. Photolysis is its dominant gas phase removal process. We have determined the gas phase absorption cross sections of 2-nitrophenol in the 295-400 nm region by using cavity ring-down spectroscopy. 2-Nitrophenol exhibits a broad absorption band over the wavelength region studied, with the peak absorption located at 345 nm. Absorption cross section values range between (2.86 ± 0.18) × 10 and (2.63 ± 0.31) × 10 cm/molecule over the 295-400 nm range. We have investigated the HONO, NO, and OH formation channels following the gas phase photolysis of 2-nitrophenol at 308 and 351 nm. Direct NO formation was not observed. HONO and OH are direct products from 2-nitrophenol photolysis. The average OH quantum yields from the photolysis of 0.5, 1.0, and 2.0 mTorr of 2-nitrophenol are 0.69 ± 0.07 and 0.70 ± 0.07 at 308 and 351 nm. The average HONO quantum yields are 0.34 ± 0.09 and 0.39 ± 0.07 at 308 and 351 nm. The OH and HONO quantum yields are independent of nitrogen carrier gas pressure in the 20-600 Torr range. Oxidant formation rate constants from 2-nitrophenol photolysis have been calculated. Discussions have been made concerning the role of 2-nitrophenol gas phase photolysis in the formation of atmospheric oxidants in regions of high anthropogenic emissions.