2017
DOI: 10.1002/qua.25419
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Dissociation of sulfur oxoacids by two water molecules studied using ab initio and density functional theory calculations

Abstract: Using ab initio [SCS‐MP2 and CCSD(T)] and density functional theory (M062X) calculations, we have studied the geometries and energies of sulfur oxoacids H2SmO6 (m = 2–4) and their monohydrated and dihydrated clusters. When including the results from previously reported disulfuric acid (H2S2O7) cases, the gas phase acidity is ordered as H2S2O6 < H2S3O6 < H2S2O7 < H2S4O6. The intramolecular H‐bonding, which may indicate the degree of structural flexibility in this molecular series, is an important factor for the… Show more

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Cited by 4 publications
(6 citation statements)
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“…It is, perhaps, surprising that such simple calculations work for these two acids, and it will be interesting to see if results for other acids can be similarly understood. Certainly, other factors such as conformational flexibility have been identified in the case of sulfur oxoacids and, more generally, the roles of entropy and finite cluster temperature need to be considered for a complete description. Nevertheless, similar arguments have recently been applied to quantitatively rationalize why the triflic acid–trimethylamine system exists as a trimethylammonium triflate ion pair (CF 3 SO 3 – ··· + HN­(CH 3 ) 3 ) in the gas phase …”
Section: Discussionmentioning
confidence: 99%
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“…It is, perhaps, surprising that such simple calculations work for these two acids, and it will be interesting to see if results for other acids can be similarly understood. Certainly, other factors such as conformational flexibility have been identified in the case of sulfur oxoacids and, more generally, the roles of entropy and finite cluster temperature need to be considered for a complete description. Nevertheless, similar arguments have recently been applied to quantitatively rationalize why the triflic acid–trimethylamine system exists as a trimethylammonium triflate ion pair (CF 3 SO 3 – ··· + HN­(CH 3 ) 3 ) in the gas phase …”
Section: Discussionmentioning
confidence: 99%
“…The same theoretical result is also obtained for halosulfonic acids (XSO 3 H, X = F, Cl, Br). 20 This is somewhat unusual insofar as many common acids require a larger number of water molecules, though a notable exception lies in several hydrated sulfur oxoacids, 9 for which calculations indicate that ionized forms represent local or global minimum energy structures at n = 2. Still, the number of water molecules needed to ionize triflic acid is predicted to be what one might term "on the low end of typical.…”
Section: ■ Introductionmentioning
confidence: 99%
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“…At selected time intervals, 5 mL aliquots of the samples were withdrawn and filtered through a 0.22 μm cellulose acetate membrane for further analysis. The speciation of thiosulfate (S 2 O 3 2− , HS 2 O 3 − , and H 2 S 2 O 3 ) (Figure S3), sulfite (SO 3 2− , HSO 3 − , and H 2 SO 3 ) (Figure S4), and polythionates (S x O 6 2− , HS x O 6 − , and H 2 S x O 6 ) 23 significantly affects their stability. Thiosulfate and polythionate decompose below pH 4.0 and above pH 8.5, respectively.…”
Section: ■ Materials and Methodsmentioning
confidence: 99%
“…At the same time, studying the system using our methodology provides new quantitative and qualitative insights into the acid-water proton transfer reaction which is also of interest in atmospheric chemistry. [20][21][22][23][24][25][26]…”
Section: Introductionmentioning
confidence: 99%