Theoretical study on excited-state intermolecular proton transfer reactions of 1H-pyrrolo[3,2-h]quinoline with water and methanol

The dynamics of the ultrafast excited-state multiple intermolecular proton transfer (PT) reactions in gas-phase complexes of 1H-pyrrolo[3,2-h]quinoline with water and methanol (PQ(H2O)n and PQ(MeOH)n , where n = 1, 2) is modeled using quantum-chemical simulations. The minimum energy ground-state structures of the complexes are determined. Molecular dynamics simulations in the first excited state are employed to determine reaction mechanisms and the time evolution of the PT processes. Excited-state dynamics results for all complexes reveal synchronous excited-state multiple proton transfer via solvent-assisted mechanisms along an intermolecular hydrogen-bonded network. In particular, excited-state double proton transfer is the most effective, occurring with the highest probability in the PQ(MeOH) cluster. The PT character of the reactions is suggested by nonexistence of crossings between ππ* and πσ* states

Temperature Dependence of Carbon Kinetic Isotope Effect for Oxidation Reaction of Ethane by Hydroxyl Radicals Under Atmospherically Relevant Conditions: Experimental and Theoretical Studies

Ethane is the second most abundant hydrocarbon in the atmosphere, after methane, impacting on air quality, human health and climate. A quantification of its effects requires accurate knowledge of sources, processes along transport, and sinks. Carbon stable isotopic ratio investigations, complementarily to concentration measurements, were demonstrated to give more insight in source apportionment and atmospheric processing of organic compounds. Yet, apportionment of atmospheric ethane sources, processing and sinks by using the $^{13}$C isotopic composition ($\delta^{13}$C) requires accurate knowledge of the stable carbon kinetic isotope effect (KIE) of its atmospheric degradation through oxidation by hydroxyl(OH) radicals. Moreover, the interpretation of tropospheric ambient data should account for the temperature dependence of KIE, since the tropospheric temperatures can vary extremely, over the range of 180-320 K. In this work, the KIE temperature dependence for the oxidation of ethane by OH radicals in the tropospherically relevant temperature range was comprehensively investigated by experimental measurements and theoretical calculations. A framework to apply the observed KIE for interpreting ambient observations is presented. Experiments to determine the KIE temperature dependence of ethane oxidation by OH radicals were carried out with natural isotope abundances in the reactant, at ambient pressure, and in a temperature range of 243 to 303 K. Propane was used as a reference compound to verify the ethane chemistry [...

Temperature dependence of stable carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals: experimental and theoretical studies

The stable carbon kinetic isotope effect (KIE) of ethane photooxidation by OH radicals was deduced by employing both laboratory measurements and theoretical calculations. The investigations were designed to elucidate the temperature dependence of KIE within atmospherically relevant temperature range. The experimental KIE was derived from laboratory compound-specific isotope analyses of ethane with natural isotopic abundance exposed to OH at constant temperature, showing ε values of 7.16 ± 0.54‰ (303 K), 7.45 ± 0.48‰ (288 K), 7.36 ± 0.28‰ (273 K), 7.61 ± 0.28‰ (263 K), 8.89 ± 0.90‰ (253 K), and 9.42 ± 2.19‰ (243 K). Compared to previous studies, a significant improvement of the measurement precision was reached at the high end of the investigated temperature range. The KIE was theoretically determined as well, in the temperature range of 150 K to 400 K, by calculating the reaction rate coefficients of 12C and singly 13C substituted ethane isotopologues applying chemical quantum mechanics together with transition state theory. Tunneling effect and internal rotations were also considered. The agreement between experimental and theoretical results for rate coefficients and KIE in an atmospherically relevant temperature range is discussed. However, both laboratory observations and computational predictions show no significant temperature dependence of the KIE for the ethane oxidation by OH radicals

Firewood residential heating – local versus remote influence on the aerosol burden

We report the first-time use of the Lagrangian particle dispersion model (LPDM) FLEXPART to simulate isotope ratios of the biomass burning tracer levoglucosan. Here, we combine the model results with observed levoglucosan concentrations and δ13C to assess the contribution of local vs. remote emissions from firewood domestic heating to the particulate matter sampled during the cold season at two measurements stations of the Environmental Agency of North Rhine-Westphalia, Germany.For the investigated samples, the simulations indicate that the largest part of the sampled aerosol is 1 to 2 d old and thus originates from local to regional sources. Consequently, ageing, also limited by the reduced photochemical activity in the dark cold season, has a minor influence on the observed levoglucosan concentration and δ13C. The retro plume ages agree well with those derived from observed δ13C (the “isotopic” ages), demonstrating that the limitation of backwards calculations to 7 d for this study does not introduce any significant bias. A linear regression analysis applied to the experimental levoglucosan δ13C vs. the inverse concentration confirms the young age of aerosol. The high variability in the observed δ13C implies that the local levoglucosan emissions are characterized by different isotopic ratios in the range of −26.3 ‰ to −21.3 ‰. These values are in good agreement with previous studies on levoglucosan source-specific isotopic composition in biomass burning aerosol. Comparison between measured and estimated levoglucosan concentrations suggests that emissions are underestimated by a factor of 2 on average. These findings demonstrate that the aerosol burden from home heating in residential areas is not of remote origin. In this work we show that combining Lagrangian modelling with isotope ratios is valuable to obtain additional insight into source apportionment. Error analysis shows that the largest source of uncertainty is limited information on isotope ratios of levoglucosan emissions. Based on the observed low extent of photochemical processing during the cold season, levoglucosan can be used under similar conditions as a conservative tracer without introducing substantial bias