Uptake of Epoxydiol Isomers Accounts for Half of the Particle-Phase Material Produced from Isoprene Photooxidation via the HO₂ Pathway

The oxidation of isoprene is a globally significant source of secondary organic material (SOM) of atmospheric particles. The relative importance of different parallel pathways, however, remains inadequately understood and quantified. SOM production from isoprene photooxidation was studied under hydroperoxyl-dominant conditions for <5% relative humidity and at 20 °C in the presence of highly acidic to completely neutralized sulfate particles. Isoprene photooxidation was separated from SOM production by using two continuously mixed flow reactors connected in series and operated at steady state. Two online mass spectrometers separately sampled the gas and particle phases in the reactor outflow. The loss of specific gas-phase species as contributors to the production of SOM was thereby quantified. The produced SOM mass concentration was directly proportional to the loss of isoprene epoxydiol (IEPOX) isomers from the gas phase. IEPOX isomers lost from the gas phase accounted for (46 ± 11)% of the produced SOM mass concentration. The IEPOX isomers comprised (59 ± 21)% (molecular count) of the loss of monitored gas-phase species. The implication is that for the investigated reaction conditions the SOM production pathways tied to IEPOX isomers accounted for half of the SOM mass concentration

Assessment of DFT for Computing Sum Frequency Generation Spectra of an Epoxydiol and a Deuterated Isotopologue at Fused Silica/Vapor Interfaces

We assess the capabilities of eight popular density functional theory (DFT) functionals, in combination with several basis sets, as applied to calculations of vibrational sum frequency generation (SFG) spectra of the atmospherically relevant isoprene oxidation product <i>trans</i>-β-isoprene epoxydiol (IEPOX) and one of its deuterated isotopologues at the fused silica/vapor interface. We use sum of squared differences (SSD) and total absolute error (TAE) calculations to estimate the performance of each functional/basis set combination in producing SFG spectra that match experimentally obtained spectra from <i>trans</i>-β-IEPOX and one of its isotopologues. Our joined SSD/TAE analysis shows that while the twist angle of the methyl <i>C</i>_3<i>v</i> symmetry axis of <i>trans</i>-β-IEPOX relative to the surface is sensitive to the choice of DFT functional, the calculated tilt angle relative to the surface normal is largely independent of the functional and basis set. Moreover, we report that hybrid functionals such as B3LYP, ωB97X-D, PBE0, and B97-1 in combination with a modest basis set, such as 6-311G­(d,p), provides good agreement with experimental data and much better performance than pure functionals such as PBE and BP86. However, improving the quality of the basis set only improves agreement with experimental data for calculations based on pure functionals. A conformational analysis, based on comparisons of calculated and experimental SFG spectra, suggests that <i>trans</i>-β-IEPOX points all of its oxygen atoms toward the silica/vapor interface

Vibrational Mode Assignment of α‑Pinene by Isotope Editing: One Down, Seventy-One To Go

This study aims to reliably assign the vibrational sum frequency generation (SFG) spectrum of α-pinene at the vapor/solid interface using a method involving deuteration of various methyl groups. The synthesis of five deuterated isotopologues of α-pinene is presented to determine the impact that removing contributions from methyl group C–H oscillators has on its SFG response. 0.6 cm^–1 resolution SFG spectra of these isotopologues show varying degrees of differences in the C–H stretching region when compared to the SFG response of unlabeled α-pinene. The largest spectral changes were observed for the isotopologue containing a fully deuterated vinyl methyl group. Noticeable losses in signal intensities allow us to reliably assign the 2860 cm^–1 peak to the vinyl methyl symmetric stretch. Furthermore, upon removing the vinyl methyl group entirely by synthesizing apopinene, the steric influence of the unlabeled C₉H₁₄ fragment on the SFG response of α-pinene SFG can be readily observed. The work presented here brings us one step closer to understanding the vibrational spectroscopy of α-pinene