Substituent Effect in the Reactions between Criegee Intermediates and 3-Aminopropanol

Abstract

Via intramolecular H atom transfer, 3-aminopropanol is more reactive toward Criegee intermediates, in comparison with amines or alcohols. Here we accessed the substituent effect of Criegee intermediates in their reactions with 3-aminopropanol. Through realtime monitoring the concentrations of two Criegee intermediates with their strong UV absorption at 340 nm, the experimental rate coefficients at 298 K (100−300 Torr) were determined to be (1.52 ± 0.08) × 10 −11 and (1.44 ± 0.22) × 10 −13 cm 3 s −1 for the reactions of 3-aminopropanol with (CH 3 ) 2 COO (acetone oxide) and CH 2 CHC(CH 3 )OO (methyl vinyl ketone oxide), respectively. Compared to our previous experimental value for the reaction with syn-CH 3 CHOO, (1.24 ± 0.13) × 10 −11 cm 3 s −1 , we can see that the methyl substitution at the anti position has little effect on the reactivity while the vinyl substitution causes a drastic decrease in the reactivity. Our theoretical calculations based on CCSD(T)-F12 energies reproduce this 2-order-of-magnitude decrease in the rate coefficient caused by the vinyl substitution. Using the activation strain model, we found that the interaction of Criegee intermediates with 3aminopropanol is weaker for the case of vinyl substitution. This effect can be further rationalized by the delocalization of the lowest unoccupied molecular orbital for the vinyl-substituted Criegee intermediates. These results would help us better estimate the impact of similar reactions like the reactions of Criegee intermediates with water vapor, some of which could be difficult to measure experimentally but can be important in the atmosphere. We also found that the B2PLYP-D3BJ/aug-cc-pVTZ calculation can reproduce the CCSD(T)-F12 reaction barrier energies within ca. 1 kcal mol −1 , indicating that the use of the B2PLYP-D3BJ method is promising for future predictions of the reactions of larger Criegee intermediates.

Experimental and Computational Studies of Criegee Intermediate syn-CH3CHOO Reaction with Hydrogen Chloride

“…This is different from the model used by Vereecken for CH 2 OO + HCl, where the (outer) barrier of the association was used as the bottleneck . In our recent study on the reaction between CIs and amino alcohol, we found that for syn -type CIs, the use of the inner barrier was valid to calculate the room temperature rate coefficient, while it failed for the anti -type CIs, such as CH 2 OO and anti -CH 3 CHOO . Considering these findings, we will use the inner barrier to calculate the rate coefficient for the present syn -CH 3 CHOO + HCl reaction.…”

“…In a recent study on the reaction of syn-type CIs with amino alcohol, we found that the explicitly correlated coupled cluster singles and doubles with perturbative triples, CCSD(T)-F12, with the F-12 optimized Dunning's correlation consistent triple valence basis set, 56 cc-pVTZ-F12 can give accurate energies. 57 Therefore, this method was also used to test the electronic energy corrections.…”

“…35 In our recent study on the reaction between CIs and amino alcohol, we found that for syn-type CIs, the use of the inner barrier was valid to calculate the room temperature rate coefficient, while it failed for the anti-type CIs, such as CH 2 OO and anti-CH 3 CHOO. 57 Considering these findings, we will use the inner barrier to calculate the rate coefficient for the present syn-CH 3 CHOO + HCl reaction. We have used the canonical TS theory with a rigid rotor harmonic oscillator approximation for all modes except the methyl group hindered rotation.…”

“…We also performed CBS extrapolation using the QCISD­(T) method by correlating both the core and valance electrons and using Dunning’s augmented core–valance aug-cc-pCVXZ (X = D, T, and Q) basis sets. , We will use the notation QCISD­(T)/CBS CV for this method. In a recent study on the reaction of syn -type CIs with amino alcohol, we found that the explicitly correlated coupled cluster singles and doubles with perturbative triples, CCSD­(T)-F12, with the F-12 optimized Dunning’s correlation consistent triple valence basis set, cc-pVTZ-F12 can give accurate energies . Therefore, this method was also used to test the electronic energy corrections.…”

Reaction Kinetics of Criegee Intermediates with Nitric Acid

“…The reactivity of CIs toward water, − ,,,,,,− alcohol, − and similar molecules , shows very strong structure dependence with the reaction rate coefficients spanning a few orders of magnitude, depending on the structure and substituent groups of the CIs. However, the reactivity of CIs toward SO 2 − and formic acid ,,− molecules has a quite weak dependence on the CI structures.…”