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Single particle cavity ring-down spectroscopy (CRDS) allows direct and continuous measurements of the extinction cross-sections for levitated micron-scale aerosol particles of constant or evolving composition. Our recent interests have concerned single particle CRDS measurements for light-absorbing particles. These measurements are made on single, spherical particles evaporating over the radius range 1500–700 nm that are levitated within a 405-nm cavity ring-down spectrometer using a linear electrodynamic quadrupole trap. Here, we quantify the accuracy and precision of our cavity ring-down time measurements and the consequences of particle motion within our electrodynamic trap. Next, we estimate the uncertainty in our particle size retrievals from angularly resolved elastic light scattering measurements for particles with a range of absorption strengths. Finally, we assess the accuracy of complex refractive index values retrieved from simultaneous ring-down time and particle size measurements. The assessments account for the impacts of shot and detector noise in the measured ring-down times, the driven particle motion within the electrodynamic trap, and particle absorption strength (for imaginary refractive indices in the range ∼0.0–0.1). The real and imaginary refractive indices are retrieved to an accuracy better than 0.005 and 0.002, respectively, for almost all absorption strengths studied, and for particles of constant or evolving composition. Although particles confined in our electrodynamic quadrupole trap undergo considerable levels of driven motion (with oscillation amplitudes of several tens of micrometers), the contribution of this motion to uncertainty in retrieved refractive indices is negligible compared to contributions from particle sizing errors.

In the context of tropospheric chemistry, Criegee intermediates denote carbonyl oxides with biradical / zwitterionic character (R1R2COO) that form during the ozonolysis of alkenes. First discovered almost 70 years ago, stabilized versions of Criegee intermediates formed via collisional removal of excess energy have interesting kinetic and mechanistic properties. The direct production and detection of these intermediates were not reported in the literature until 2008. However, recent advances in their generation through the ultraviolet irradiation of the corresponding diiodoalkanes in excess O2 and detection by various spectroscopic techniques (photoionization, ultraviolet, infrared, microwave and mass spectrometry) have shown that these species can react rapidly with closed shell molecules, in many cases at or exceeding the classical gas-kinetic limit, via multiple reaction pathways. These reactions can be complex, and laboratory measurements of products and the temperature and pressure dependence of the reaction kinetics have also revealed unusual behaviour. The potential role of these intermediates in atmospheric chemistry is significant, altering models of the oxidising capacity of the Earth's atmosphere and the rate of generation of secondary organic aerosol.

Cavity ring-down spectroscopy (CRDS) of single, optically manipulated aerosol particles affords quantitative retrieval of refractive indices for particles of fixed or evolving composition with high precision. Here, we quantify the accuracy with which refractive index determinations can be made by CRDS for single particles confined within the core of a Bessel laser beam and how that accuracy is degraded as the particle size is progressively reduced from the coarse mode (>1 μm radius) to the accumulation mode (n, and imaginary, κ, components of the refractive index can be determined for a single aerosol particle. Published with license by American Association for Aerosol Research Read the transcript Watch the video on Vimeo

The use of cavity ring down spectroscopy to retrieve aerosol complex refractive index from optical property measurements has seen increasing popularity over the past few years. However, few studies have looked at the limit which sources of error and uncertainty inherent in the cavity ring down method place on the accuracy with which the refractive index can be retrieved. In this paper, we consider both experimental sources of error and those which compromise the theoretical models against which measurements are compared, both reviewing previously published work and presenting new data. Our results show that for absolute measurements made using single-cavity instruments, factors such as uncertainty in the length of the ring down cavity occupied by aerosol and the counting efficiency of the CPC can introduce an error of ∼2.5% into the real part of the refractive index retrieved from experiment. This is significantly higher than the typical 1% error quoted in previously published work. We note that due to th...

The HCl(v' = 0, J') rotational state distributions produced in the photoinitiated reactions of ground spin-orbit state Cl(2P3/2) atoms with the organic heterocycles oxirane (c-C2H4O), thiirane (c-C2H4S) and oxetane (c-C3H6O) have been measured using the technique of 2 + 1 resonance-enhanced multiphoton ionization in a time-of-flight mass spectrometer. In contrast to previous studies of H-atom abstraction dynamics by Cl atoms with linear functionalized molecules, the nascent HCl(v' = 0, J') products of the reactions of the three-membered heterocycles oxirane and thiirane are formed rotationally cold, with mean rotational energies of (0.28 ± 0.02) kcal mol-1 and (0.31 ± 0.02) kcal mol-1, respectively. The reaction of Cl atoms with the four-membered heterocycle oxetane, however, results in more rotationally excited HCl(v' = 0, J') products for which = (0.78 ± 0.03) kcal mol-1. Ab initio calculations were performed at the G2//MP2/6-311G(d,p) level to characterize molecular complexes and transiti...