Do Hydroxyl Radical−Water Clusters, OH(H2O)n, n = 1−5, Exist in the Atmosphere?

It has been speculated that the presence of OH(H2O)n clusters in the troposphere could have significant effects on the solar absorption balance and the reactivity of the hydroxyl radical. We have used the G3 and G3B3 model chemistries to model the structures and predict the frequencies of hydroxyl radical/water clusters containing one to five water molecules. The reaction between hydroxyl radical clusters and methane was examined as a function of water cluster size to gain an understanding of how cluster size affects the hydroxyl radical reactivity.

Vibrational Relaxation of 13CO2(v2) by Atomic Oxygen

Carbon dioxide (CO2) has been of recent interest due to the issue of greenhouse cooling in the upper atmosphere by species such as CO2 and NO. In the Earth’s upper atmosphere, between altitudes of 75 and 110 km, a collisional energy exchange occurs between CO2 and atomic oxygen, which promotes a population of ground state CO2 to the bend excited state. The relaxation of CO2 following this excitation is characterized by spontaneous emission of 15-μm. Most of this energy is emitted away from Earth. Due to the low density in the upper atmosphere, most of this energy is not reabsorbed and thus escapes into space, leading to a local cooling effect in the upper atmosphere. To determine the efficiency of the CO2- O atom collisional energy exchange, transient diode laser absorption spectroscopy was used to monitor the population of the first vibrationally excited state, 13CO2(0110) or ν2, as a function of time. The rate coefficient, kO(ν2), for the vibrational relaxation 13CO2 (ν2)-O was determined by fitting laboratory measurements using a home-written linear least squares algorithm. The rate coefficient, kO(ν2), of the vibrational relaxation of 13CO2(ν2), by atomic oxygen at room temperature was determined to be (1.6 ± 0.3 x 10-12 cm3 s-1), which is within the uncertainty of the rate coefficient previously found in this group for 12CO2(ν2) relaxation. The cold temperature kO(ν2) values were determined to be: (2.1 ± 0.8) x 10-12 cm3 s-1 at Tfinal = 274 K, (1.8 ± 0.3) x 10-12 cm3 s-1 at Tfinal = 239 K, (2 ± 1) x 10-12 cm3 s-1 at Tfinal = 208 K, and (1.7 ± 0.3) x 10-12 cm3 s-1 at Tfinal = 186 K. These data did not show a definitive negative temperature dependence comparable to that found for 12CO2 previously.