Conformational Analysis of Sulfur Mustard from Molecular Mechanics, Semiempirical, and ab Initio Methods

Donovan, William H.; Famini, George R.

doi:10.1021/j100065a021

Cited by 17 publications

(10 citation statements)

References 15 publications

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“…Twenty-two conformers of SM were located using the B3LYP/6-311++G(2d,2p) method (Figure S1). Conformer A is the most stable one, and this is in agreement with previous studies. ,, However, the relative stability of the other conformers differ from the results of Lach and co-workers …”

Section: Resultssupporting

confidence: 91%

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Theoretical Study of the Microhydration the Chemical Warfare Agent Sulfur Mustard

2020

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A microhydration study of sulfur mustard (SM) was carried out using M06-2X, B3LYP, B3LYP-D3, and MP2 levels of theory with the 6-311++G(2d,2p) basis set. The changes in energetics, structural parameters and vibrational wavenumbers following the addition of up to three discrete water molecules to SM were analyzed. We observed slight changes in the geometry of SM upon microhydration. The stability of hydrated clusters is due to weak C–H···O–H hydrogen bonds. The free energy change for the formation of the clusters is positive at room temperature and becomes exergonic when the temperature decreases. The infrared stretchings of C–Cl of SM and O–H of water are redshifted upon the addition of water molecules. The findings from this work add to the literature of hydrated SM and can be useful in its detection and subsequent destruction.

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Section: Resultssupporting

confidence: 91%

“…Conformer A is the most stable one, and this is in agreement with previous studies. 47,65,66 However, the relative stability of the other conformers differ from the results of Lach and co-workers. 47 A was used as the free SM molecule to which discrete water molecules were subsequently added.…”

Section: Computational Detailsmentioning

confidence: 60%

Theoretical Study of the Microhydration the Chemical Warfare Agent Sulfur Mustard

2020

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“…The calculated hydration energy of 1 is 72.0 kcal/mol (6-31‫ם‬G*), which is compared with the experimental values of 61-87 kcal/mol for alkylsulfonium ions [29]. The conformations of 2 and 3 in Figure 1 are consistent with the most stable conformation calculated for sulfur mustard [12].…”

Section: Molecular Structuressupporting

confidence: 59%

Ab initio GB study of chemical intermediates in solution; Ethylenesulfonium ion in hydrolysis of 2-chloroethyl methyl sulfide

et al. 1998

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“…The exact value of E~ol calculated depends on both molecular conformation and the solvation model selected. For the most reliable estimate of E~,,i, we select the lowest energy conformation of HD, namely AGGA [ 13]. Applying the AM I-SM2 model to this system delivers an E~,,~ value of -3.85 kcal/mol, in excellent agreement with experiment.…”

Section: Aqueous Solution Calculationsmentioning

confidence: 69%

Theoretical investigation of isotopic scrambling mechanisms in 2-chloroethyl methyl sulfide

Donovan

1995

Struct Chem

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Ab initio and semiempirical molecular orbital calculations have been applied to study the concerted and stepwise isotopic scrambling mechanisms of 2-chloroethyl methyl sulfide in the gas phase and in aqueous solution. The calculations reveal the structural details of the reactants, transition structures, and intermediates involved in this reaction and provide relative energy estimates. The concerted mechanism is found to be competitive with the stepwise mechanism in the gas phase, but the stepwise mechanism is favored in aqueous solution as no true transition structure for the concerted mechanism could be found using the solvation models. A combined approach of evaluating solvation energies with the generalized-Born-plus-surface-tensions SMx solvation models of Cramer and Truhlar at ab initio optimized geometries is found to deliver the best agreement with experimentally determined reaction barriers. Together with the recent experimental results of McManus and co-workers, the present study provides insights into the controlling factors involved in the elementary reaction steps of sulfur mustards and a solid foundation for investigations into more complex reactions of related compounds.

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Conformational Analysis of Sulfur Mustard from Molecular Mechanics, Semiempirical, and ab Initio Methods

Cited by 17 publications

References 15 publications

Theoretical Study of the Microhydration the Chemical Warfare Agent Sulfur Mustard

Theoretical Study of the Microhydration the Chemical Warfare Agent Sulfur Mustard

Ab initio GB study of chemical intermediates in solution; Ethylenesulfonium ion in hydrolysis of 2-chloroethyl methyl sulfide

Theoretical investigation of isotopic scrambling mechanisms in 2-chloroethyl methyl sulfide

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