Theoretical study of the microhydration of 1‐chloro and 2‐chloro ethanol as a clue for their relative propensity toward dehalogenation

Petsis, George; Salta, Zoi; Kosmas, Agnie M.; Ventura, Oscar N.

doi:10.1002/qua.25931

Cited by 6 publications

(5 citation statements)

References 69 publications

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“…Many different DFT methods exist, and several papers have been published recently on the accuracy of such procedures [25][26][27][28][29][30][31][32][33][34]. Based on our previous experience [25,36], we have chosen the M06 method [37], one of the components of the Minnesota functional suite, by Truhlar and collaborators. The method depends on a series of parameters optimized with different basis sets.…”

Section: Methodsmentioning

confidence: 99%

Enthalpies of formation of the benzyloxyl, benzylperoxyl, hydroxyphenyl radicals and related species on the potential energy surface for the reaction of toluene with the hydroxyl radical

Ventura¹,

Kieninger²,

Salta

et al. 2019

Theor Chem Acc

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The reaction of toluene (T) with OH • produces addition products as well as the benzyl radical (TR). TR can react with OH • or O2 to produce oxygenated species, for many of which there is no experimental information available. We present here theoretically determined heats of formation (HFs) of 17 such species using the non-isodesmic reactions on the potential energy surface (PES) of TR+O2 and T+OH • +O2. For those species the experimental HFs of which are known, we obtained a good correlation between experimental and theoretical values at the G4 (r 2 =0.999) and M06/cc-pVQZ (r 2 =0.997) levels, thus showing the goodness of the methods used. Previously unknown HFs of other radicals (benzyloxyl, spiro [1,2-dioxetane benzyl], hydroxyphenyl, and benzylperoxyl) and closed shell species (salicylic alcohol, benzo[b]oxetane and p-hydroxy cyclohexa-2,5dienone) were later determined using those methods.

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Section: Methodsmentioning

confidence: 99%

Enthalpies of formation of the benzyloxyl, benzylperoxyl, hydroxyphenyl radicals and related species on the potential energy surface for the reaction of toluene with the hydroxyl radical

Ventura¹,

Kieninger²,

Salta

et al. 2019

Theor Chem Acc

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“…The conclusion is that if any solvent effect is observed, it is not due to bulk polarization by the solvent but, if at all, by the presence of one or two auxiliary water molecules which may move barriers downwards, as it is known to occur in other reactions (see, for instance, ref. [50]).…”

Section: Resultsmentioning

confidence: 99%

Kinetics and thermodynamics of the hydroxylation products in the photodegradation of the herbicide Metolachlor

Salta

Kosmas

Ventura

2020

Pure and Applied Chemistry

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Electronic structure calculations have been performed to determine the thermochemistry and kinetics of the reaction between OH and the radicals of the S enantiomer of the herbicide Metolachlor, 2-chloro-N-(2-methyl-6-ethylphenyl)-N(2-methoxy-1-methylethyl) acetamide (MC), produced by photoinduced breaking of the C–Cl bond. Both density functional and ab initio composite methods were employed to calculate the structure of reactants, intermediates, transition states and products, in gas phase and in aqueous solution. The expected relative abundance of each product was calculated and compared to the experimentally observed concentrations. It is shown that a combination of thermodynamic and kinetic characteristics interplay to produce the expected theoretical abundances, which turn out to be in agreement with the experimentally observed distribution of products.

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“…The molecular geometries of the various conformers and rotamers of 1-chloroethanol and 2-chloroethanol [36,37] were optimized with the Gaussian 09 software package (Gaussian, Inc., Wallingford, CT, USA) [38] at the MP2 level of theory with the aug-cc-pVTZ basis set (Tables S1-S7). The same software with the same level of theory and basis set was also used to calculate the permanent dipole moments µ [39] and their components with respect the principal axes of inertia µ A , µ B , and µ C ; the rotational constants A, B, and C; and the relative energies E for the various conformers or rotamers.…”

Section: Conformers and Ab Initio Calculationsmentioning

confidence: 99%

Conformer Selection by Electrostatic Hexapoles: A Theoretical Study on 1-Chloroethanol and 2-Chloroethanol

et al. 2022

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The electrostatic hexapole is a versatile device that has been used for many years in gas-phase experiments. Its inhomogeneous electric field has been employed for many purposes such as the selection of rotational states, the selection of clusters, the focusing of molecular beams, and molecular alignment as a precursor for molecular orientation. In the last few years, the hexapolar electric field has been demonstrated to be able to control the conformer composition of molecular beams. The key point is that conformers, where the component of the permanent electric dipole moment with respect to the largest of the principal axes of inertia is close to zero, require more intense hexapolar electric fields to be focused with respect to the other conformers. Here, we simulated the focusing curves of the conformers of 1-chloroethanol and 2-chloroethanol under hypothetical beam conditions, identical for all conformers, in a hypothetical and realistic experimental setup with three different hexapole lengths: 0.5, 1, and 2 m. The objective was to characterize this selection process to set up collision experiments on conformer-selected beams that provide information on the van der Waals clusters formed in collision processes.

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Theoretical study of the microhydration of 1‐chloro and 2‐chloro ethanol as a clue for their relative propensity toward dehalogenation

Cited by 6 publications

References 69 publications

Enthalpies of formation of the benzyloxyl, benzylperoxyl, hydroxyphenyl radicals and related species on the potential energy surface for the reaction of toluene with the hydroxyl radical

Enthalpies of formation of the benzyloxyl, benzylperoxyl, hydroxyphenyl radicals and related species on the potential energy surface for the reaction of toluene with the hydroxyl radical

Kinetics and thermodynamics of the hydroxylation products in the photodegradation of the herbicide Metolachlor

Conformer Selection by Electrostatic Hexapoles: A Theoretical Study on 1-Chloroethanol and 2-Chloroethanol

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