Airborne compact rotational Raman lidar for temperature measurement.

We developed an airborne compact rotational Raman lidar (CRL) for use on the University of Wyoming King Air (UWKA) aircraft to obtain two-dimensional (2D) temperature disman tributions. It obtained fine-scale 2D temperature distributions within 3 km below the aircraft for the first time during the PECAN (Plains Elevated Convection At Night) campaign in 2015. The CRL provided nighttime temperature measurements with a random error of <0.5 K within 800 m below aircraft at 45 m vertical and 1000 m horizontal resolution. The temperatures obtained by the CRL and a radiosonde agreed. Along with water vapor and aerosol measurements, the CRL provides critical parameters on the state of the lower atmosphere for a wide range of atmospheric research.

Wyoming Cloud Lidar: instrument description and applications.

The Wyoming Cloud Lidar (WCL), a compact two-channel elastic lidar, was designed to obtain cloud measurements together with the Wyoming Cloud Radar (WCR) on the University of Wyoming King Air and the National Science Foundation/National Center of Atmospheric Research C-130 aircraft. The WCL has been deployed in four field projects under a variety of atmospheric and cloud conditions during the last two years. Throughout these campaigns, it has exhibited the needed reliability for turn-key operation from aircraft. We provide here an overview of the instrument and examples to illustrate the measurements capability of the WCL. Although the WCL as a standalone instrument can provide unique measurements for cloud and boundary layer aerosol studies, the synergy of WCL and WCR measurements coupled with in situ sampling from an aircraft provide a significant step forward in our ability to observe and understand cloud microphysical property evolution.

Near-IR cavity ringdown spectroscopy and kinetics of the isomers and conformers of the butyl peroxy radical.

Cavity ringdown spectra of butyl peroxy radicals have been obtained for their A-X electronic transition in the near-IR. The radicals were produced by two independent chemical methods, allowing unambiguous assignment of the spectra of the four butyl peroxy isomers with probable conformer assignments also possible for a number of cases. Using the analyzed spectra semiquantatively, isomer specific rate constants for butyl peroxy self-reaction were measured, as was the relative reactivity of the various sorts of H atoms in butane to Cl atom attack.

Observation of the A-X electronic transition of the 1-C3H7O2 and 2-C3H7O2 radicals using cavity ringdown spectroscopy.

Cavity ringdown spectra of the A-X electronic transition of the 1-propyl and 2-propyl peroxy radicals are reported. Spectroscopic assignments are facilitated by implementing several production mechanisms, either isomer-specific or not. Assignments of specific spectral lines to particular conformers of a given isomer are suggested. Observations on the temporal decay of the various species are reported.

Theoretical determinations of the ambient conformational distribution and unimolecular decomposition of n-propylperoxy radical.

The conformational distribution and unimolecular decomposition pathways for the n-propylperoxy radical have been generated at the CBS-QB3, B3LYP/6-31+G and mPW1K/6-31+G levels of theory. At each of the theoretical levels, the 298 K Boltzmann distributions and rotational profiles indicate that all five unique rotamers of the n-propylperoxy radical can be expected to be present in significant concentrations at thermal equilibrium. At the CBS-QB3 level, the 298 K distribution of rotamers is predicted to be 28.1, 26.4, 19.6, 14.0, and 11.9% for the gG, tG, gT, gG', and tT conformations, respectively. The CBS-QB3 C-OO bond dissociation energy (DeltaH298 K) for the n-propylperoxy radical has been calculated to be 36.1 kcal/mol. The detailed CBS-QB3 potential energy surface for the unimolecular decomposition of the n-propylperoxy radical indicates that important bimolecular products could be derived from two 1,4-H transfer mechanisms available at T < 500 K, primarily via an activated n-propylperoxy adduct.