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The reactions of thioformaldehyde (H 2 CS) with OH radicals and assisted by a single water molecule have been investigated using high level ab initio quantum chemistry calculations. The H 2 CS + ˙OH reaction can in principle proceed through: (1) abstraction, and (2) addition pathways. The barrier height for the addition reaction in the absence of a catalyst was found to be −0.8 kcal mol −1 , relative to the separated reactants, which has a ∼1.0 kcal mol −1 lower barrier than the abstraction channel. The H 2 CS + ˙OH reaction assisted by a single water molecule reduces the barrier heights significantly for both the addition and abstraction channels, to −5.5 and −6.7 kcal mol −1 respectively, compared to the un-catalyzed H 2 CS + ˙OH reaction. These values suggest that water lowers the barriers by ∼6.0 kcal mol −1 for both reaction paths. The rate constants for the H 2 CS⋯H 2 O + ˙OH and OH⋯H 2 O + H 2 CS bimolecular reaction channels were calculated using Canonical Variational Transition state theory (CVT) in conjunction with the Small Curvature Tunneling (SCT) method over the atmospherically relevant temperatures between 200 and 400 K. Rate constants for the H 2 CS + ˙OH reaction paths for comparison with the H 2 CS + ˙OH + H 2 O reaction in the same temperature range were also computed. The results suggest that the rate of the H 2 CS + ˙OH + H 2 O reaction is slower than that of the H 2 CS + ˙OH reaction by ∼1–4 orders of magnitude in the temperatures between 200 and 400 K. For example, at 300 K, the rates of the H 2 CS + ˙OH + H 2 O and H 2 CS + ˙OH reactions were found to be 2.2 × 10 −8 s −1 and 6.4 × 10 −6 s −1 , respectively, calculated using [OH] = 1.0 × 10 6 molecules cm −3 , and [H 2 O] = 8.2 × 10 17 molecules cm −3 (300 K, RH 100%) atmospheric conditions. Electronic structure calculations on the H 2 C(OH)S˙ product in the presence of 3 O 2 were also performed. The results show that H 2 CS is removed from the atmosphere primarily by reacting with ˙OH and O 2 to form thioformic acid, HO 2 , formaldehyde, and SO 2 as the main end products.
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Dynamics of the isotope exchange reaction of D with H3+, H2D+, and D2H+
We have measured the merged-beams rate coefficient for the titular isotope exchange reactions as a function of the relative collision energy in the range of ∼3 meV–10 eV. The results appear to scale with the number of available sites for deuteration. We have performed extensive theoretical calculations to characterize the zero-point energy corrected reaction path. Vibrationally adiabatic minimum energy paths were obtained using a combination of unrestricted quadratic configuration interaction of single and double excitations and internally contracted multireference configuration interaction calculations. The resulting barrier height, ranging from 68 meV to 89 meV, together with the various asymptotes that may be reached in the collision, was used in a classical over-the-barrier model. All competing endoergic reaction channels were taken into account using a flux reduction factor. This model reproduces all three experimental sets quite satisfactorily. In order to generate thermal rate coefficients down to 10 K, the internal excitation energy distribution of each H3+ isotopologue is evaluated level by level using available line lists and accurate spectroscopic parameters. Tunneling is accounted for by a direct inclusion of the exact quantum tunneling probability in the evaluation of the cross section. We derive a thermal rate coefficient of <1×10−12 cm3 s−1 for temperatures below 44 K, 86 K, and 139 K for the reaction of D with H3+, H2D+, and D2H+, respectively, with tunneling effects included. The derived thermal rate coefficients exceed the ring polymer molecular dynamics prediction of Bulut et al. [J. Phys. Chem. A 123, 8766 (2019)] at all temperatures.
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- Award ID(s):
- 2002461
- PAR ID:
- 10593484
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 154
- Issue:
- 8
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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