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Laboratory studies can provide important insights into the processes that occur at the scale of individual particles in ambient aerosol. We examine the accuracies of measurements of core physicochemical properties of aerosols that can be made in single particle studies and explore the impact of these properties on the microscopic processes that occur in ambient aerosol. Presenting new measurements, we examine here the refinements in our understanding of aerosol hygroscopicity, surface tension, viscosity and optical properties that can be gained from detailed laboratory measurements for complex mixtures through to surrogates for secondary organic atmospheric aerosols.

Ultrafast transient electronic and vibrational absorption spectroscopy (TEAS and TVAS) of 2′-deoxy-cytidine (dC) and 2′-deoxy-thymidine (dT) dissolved in chloroform examines their excited-state dynamics and the recovery of ground electronic state molecules following absorption of ultraviolet light. The chloroform serves as a weakly interacting solvent, allowing comparisons to be drawn with prior experimental studies of the photodynamics of these nucleosides in the gas phase and in polar solvents such as water. The pyrimidine base nucleosides have some propensity to dimerize in aprotic solvents, but the monomer photochemistry can be resolved clearly and is the focus of this study. UV absorption at a wavelength of 260 nm excites a 1ππ* ← S0 transition, but prompt crossing of a significant fraction (50% in dC, 17% in dT) of the 1ππ* population into a nearby 1nπ* state is too fast for the experiments to resolve. The remaining flux on the 1ππ* state leaves the vertical Franck–Condon region and encounters a conical intersection with the ground electronic state of ethylenic twist character. In dC, the 1ππ* state decays to the ground state with a time constant of 1.1 ± 0.1 ps. The lifetime of the 1nπ* state is much longer in the canonical forms of both molecules: recovery of the ground state population from these states occurs with time constants of 18.6 ± 1.1 ps in amino-oxo dC and ∼114 ps in dT, indicating potential energy barriers to the 1nπ*/S0 conical intersections. The small fraction of the imino-oxo tautomer of dC present in solution has a longer-lived 1nπ* state with a lifetime for ground state recovery of 193 ± 55 ps. No evidence is found for photo-induced tautomerization of amino-oxo dC to the imino-oxo form, or for population of low lying triplet states of this nucleoside. In contrast, ∼8% of the UV-excited dT molecules access the long-lived T1 (3ππ*) state through the 1nπ* state. The primary influence of the solvent appears to be the degree to which it destabilizes the states of 1nπ* character, with consequences for the lifetimes of these states as well as the triplet state yields.

We report new results on the absorption cross sections and photochemical quantum yields for radical (H + HCO) production from formaldehyde in the wavelength interval from 308-320 nm, obtained at resolutions of better than 0.1 nm. The absorption cross sections, measured at resolutions close to the limit for Doppler broadening of HCHO, show rotationally resolved fine structure, with maximum values higher than those obtained in previous, lower resolution, studies. In this wavelength region, absorption cross sections peak at 2.3 x 10(-19) cm2 molecule(-1), but band-integrated values are in excellent accord with previous measurements. HCO absorption coefficients, measured by cavity ring-down spectroscopy following UV photolysis of HCHO at wavelengths across the 2(0)(1)5(0)(1), 2(0)(2)4(0)(3) and 2(0)(3)4(0)(1) bands of the A1A2-X1A1 transition, generally mimic the parent absorption band profiles. Division of these absorption coefficients by the high resolution parent absorption cross sections gives relative quantum yields for the H + HCO radical product channel that can be put on an absolute scale using single-wavelength literature values. These quantum yields are observed to show some variation with parent excitation wavelength (and thus with excited vibronic level). Addition of 200 Torr of N2 increases the HCO quantum yields.