Publications by authors named "Kimberly R Daley"

Organosulfates formed from heterogeneous reactions of organic-derived oxidation products with sulfate ions can account for >15% of secondary organic aerosol (SOA) mass, primarily in submicron particles with long atmospheric lifetimes. However, fundamental understanding of organosulfate molecular structures is limited, particularly at atmospherically relevant acidities (pH = 0-6). Herein, for 2-methyltetrol sulfates (2-MTSs), an important group of isoprene-derived organosulfates, protonation state and vibrational modes were studied using Raman and infrared spectroscopy, as well as density functional theory (DFT) calculations of vibrational spectra for neutral (RO-SOH) and anionic/deprotonated (RO-SO) structures.

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Ultrafast picosecond time scale two-dimensional infrared (2D-IR) spectroscopy of a new water-soluble transition metal complex acting as a vibrational probe shows that over a range of concentration and poly(ethylene glycol) (PEG) molecular mass (2000, 8000, and 20000 Da) the time scale of the sensed hydration dynamics differs negligibly from bulk water (DO). PEG is well-known to establish a highly stable hydration shell because the spacing between adjacent ethereal oxygens nearly matches water's hydrogen-bonding network. Although these first-shell water molecules are likely significantly retarded, they present an interface to subsequent hydration shells and thus diminish the largely entropic perturbation to water's orientational dynamics.

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