Experimental and computational studies of Criegee intermediate reactions with NH3 and CH3NH2

Chhantyal-Pun, Rabi; Shannon, Robin J.; Tew, David P.; Caravan, Rebecca L.; Duchi, Marta; Wong, Callum; Ingham, Aidan; Feldman, Charlotte; McGillen, Max R.; Khan, M. Anwar H.; Antonov, Ivan O.; Rotavera, Brandon; Ramasesha, Krupa; Osborn, David L.; Taatjes, Craig A.; Percival, Carl J.; Shallcross, Dudley E.; Orr-Ewing, Andrew J.

doi:10.1039/c8cp06810k

Cited by 47 publications

(63 citation statements)

References 57 publications

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“…5, Top and Right Inset). These products are consistent with characteristic HCO 2 -loss (= protonated CI) and HO 2 -loss daughter ions (DIs) from the dissociative photoionization of the predicted functionalized hydroperoxide reaction product, HPBF (18,19,44). The formation of the hydroperoxide product is further evidenced by the agreement between the observed and calculated vertical ionization energies and appearance energies for the m/z 99 DI (further details in SI Appendix).…”

Section: Resultssupporting

confidence: 74%

Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate

Caravan

Vansco

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

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198

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Isoprene has the highest emission into Earth’s atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have revealed that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield from isoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester, J. Chem. Phys. 149, 44309 (2018)] but suggest different conformer distributions under jet-cooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only the syn-conformers are observed; anti-conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction of syn-MVK-oxide with SO2 and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. We determine products through complementary multiplexed photoionization mass spectrometry, observing SO3 and identifying organic hydroperoxide formation from reaction with SO2 and formic acid, respectively. The tropospheric implications of these reactions are evaluated using a global chemistry and transport model.

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Section: Resultssupporting

confidence: 74%

Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate

Caravan

Vansco

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

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198

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“…1,2,3,4,5 In particular, the CCSD(T) method (i.e., CC with single, double, and quasiperturbative triple excitations) 6,78 has been extensively used for obtaining reaction barrier heights in a wide range of chemical systems (for a few recent examples see refs. 9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24). With the increase in available computational power and efficiency of quantum chemical codes, the calculation of reaction barrier heights with higher-order CC methods (normally up to CCSDT(Q)) has become more prevalent over the past decade.…”

Section: Introductionmentioning

confidence: 99%

Highly Accurate CCSDT(Q)/CBS Reaction Barrier Heights for a Diverse Set of Transition Structures: Basis Set Convergence and Cost-Effective Approaches for Estimating Post-CCSD(T) Contributions

Karton

2019

J. Phys. Chem. A

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The ability to accurately calculate reaction barrier heights is of central importance to many areas of chemistry. We report an extensive study examining the basis set convergence of post-CCSD(T) contributions (up to CCSDT(Q)) for a diverse set of 28 reaction barrier heights. In contrast to previous studies, we focus here on larger transition structures (TSs) involving 4-7 non-hydrogen atoms. The set of reaction barrier heights includes pericyclic, bipolar cycloaddition, cycloreversion, and multiple proton transfer reactions. We find that in most cases post-CCSD(T) contributions converge rapidly towards the basis set limit, such that even double-z and truncated double-z basis sets provide useful estimates of the T-(T) and (Q) contributions, respectively. In addition, we find that due to the tendency of these small basis sets to systematically underestimate the T-(T) and (Q) components, scaling is an effective approach for improving performance. For example, scaling the T-(T)/cc-pVDZ contribution by 1.25 results in an RMSD of merely 0.4 kJ mol -1 relative to basis set limit reference values from W3lite-F12 theory. Similarly, calculating the (Q) contribution with a cc-pVDZ basis set without d functions and scaling by 1.6 results in an RMSD of 0.5 kJ mol -1 . We also examine the magnitude of post-CCSD(T) contributions for a wide range of TSs. We find that for pericyclic, bipolar cycloaddition, and multiple proton transfer reactions there is an effective cancellation between the T-(T) and (Q) components (i.e., they have opposite signs and are of similar magnitude), such that overall post-CCSD(T) contributions to the reaction barrier heights are below ~1 kJ mol -1 (in absolute value). However, for the barrier heights of cycloreversion reactions, the T-(T) and (Q) components are both negative and large and consequentially post-CCSD(T) contributions reduce the reaction barrier heights by significant amounts ranging between 4.1-6.7 kJ mol -1 .

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“…These CIs have been identified with various detection methods, like photoionization mass spectrometry (Taatjes et al, 2013), infrared action (Liu et al, 2014b) and absorption Lin et al, 2015) spectroscopy, UV-visible spectroscopy (Beames et al, 2013;Sheps, 2013;Liu et al, 2014a;Ting et al, 2014;Smith et al, 40 2014;Chang et al, 2016), microwave spectroscopy (McCarthy et al, 2013;Nakajima et al, 2015), etc. In addition, utilizing the direct detection of CIs, a number of kinetic investigations of CI reactions, e.g., with SO 2 (Huang et al, 2015), water vapor (Chao et al, 2015), alcohols (Chao et al, 2019), thiols (Li et al, 2019), amines (Chhantyal-Pun et al, 2019), carbonyl molecules (Taatjes et al, 2012), and organic (Welz et al, 2014) and inorganic (Foreman et al, 2016) acids, etc., have been reported (Lee, 2015;Osborn and Taatjes, 2015;Lin and Chao, 2017;Khan et al, 2018). 45…”

Section: Ch I → Ch I I ( R 1 )mentioning

confidence: 99%

Kinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorption

Kuo¹,

Weber²,

Fittschen³

et al. 2020

Preprint

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Abstract. Criegee intermediates (CIs) are formed in the ozonolysis of unsaturated hydrocarbons and play a role in atmospheric chemistry as a non-photolytic OH source or a strong oxidant. Using a relative rate method in an ozonolysis experiment, Newland et al. [Atmos. Chem. Phys., 15, 9521&#8211;9536, 2015] reported high reactivity of isoprene-derived Criegee intermediates towards dimethyl sulfide (DMS) relative to that towards SO2 with the ratio of the rate coefficients kDMS+CI&#8201;/&#8201;kSO2+CI&#8201;=&#8201;3.5&#8201;&#177;&#8201;1.8. Here we reinvestigated the kinetics of DMS reactions with two major Criegee intermediates formed in isoprene ozonolysis, CH2OO and methyl vinyl ketone oxide (MVKO). The individual CI was prepared following reported photolytic method with suitable (diiodo) precursors in the presence of O2. The concentration of CH2OO or MVKO was monitored directly in real time through their intense UV-visible absorption. Our results indicate the reactions of DMS with CH2OO and MVKO are both very slow; the upper limits of the rate coefficients are 4 orders of magnitude smaller than that reported by Newland et al. These results suggest that the ozonolysis experiment could be complicated such that interpretation should be careful and these CIs would not oxidize atmospheric DMS at any substantial level.

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Experimental and computational studies of Criegee intermediate reactions with NH₃ and CH₃NH₂

Abstract: The significance of removal of atmospheric ammonia and amines by reaction with Criegee intermediates is assessed by kinetic studies.

Cited by 47 publications

References 57 publications

Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate

Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate

Highly Accurate CCSDT(Q)/CBS Reaction Barrier Heights for a Diverse Set of Transition Structures: Basis Set Convergence and Cost-Effective Approaches for Estimating Post-CCSD(T) Contributions

Kinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorption

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