The origin and magnitude of intramolecular quasi-cyclic S⋯O and S⋯S interactions revisited: A computational study

Si, Mrinal Kanti; Lo, Rabindranath

doi:10.1016/j.cplett.2015.04.036

Cited by 25 publications

(25 citation statements)

References 43 publications

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“…The electron density (ρ) and Laplacian electron density (∇ 2 ρ) values corroborate the MESP analysis to achieve the stability of the conjugate base of acids (Table TS4). − The V ( r )/ G ( r ) ratio indicates that the noncovalent interaction between the CSe group and the CP – of 1 is purely electrostatic in nature. The electron density values calculated for 6 reveals that the interaction between the CSe group and the CP – of 6 is predominantly covalent in nature (Figure and Table TS4).…”

Section: Resultsmentioning

confidence: 99%

Rational Design of Mono- and Dianions as Superacids Through π-Hole Interaction: Implications for Lithium and Magnesium Ion Batteries

Ganguly

2018

J. Phys. Chem. C

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Nature helps generate multiply charged negative ions in abundance. Such negatively charged ions are stable as crystals with charge compensating cations, but in solution, they are protected with solvent molecules. In the gas phase, such multicharged anions are not stable due to strong electrostatic repulsion between the extra electrons. Therefore, the generation of multicharged anions without the influence of environment has been of great interest. The DFT calculations reveal that the π-hole interactions can stabilize the anion of acid using the selenoaldehydic group attached to the cyclopentadiene ring to make them superacids. This strategy helped to generate the stability of dianions without any influence of environmental conditions. It is known that most electrolytes used in Li-ion batteries contain halogens, which are, however, toxic in nature. The designed superacids can also be exploited as lithium ion batteries. These stable dianions showed the binding energies of lithium ions (5.8 and 63.6 kcal/mol) at M06-2X/6-311+G(2d,p) level of theory and can be considered as an efficient electrolyte in lithium ion battery. The study was extended with magnesium ion, which also showed promise to function as an efficient electrolyte in a magnesium ion battery using such anions.

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Section: Resultsmentioning

confidence: 99%

Rational Design of Mono- and Dianions as Superacids Through π-Hole Interaction: Implications for Lithium and Magnesium Ion Batteries

Ganguly

2018

J. Phys. Chem. C

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“…[71] The positive values of the Laplacian electron densities (r 2 ρ) for all the Li…H than Li…C BCPs show the decreasing electron density which is characteristic of closed-shell interactions and indicate electrostatic nature of such interactions (Table 13). [72,73] The calculated Laplacian and σ(r) values for Li…H than Li…C BCPs in H 2 , CO 2 , CO adsorbed complexes indicate that the Li…C bond in CO 2 adsorbed complex is stronger than in H 2 , CO adsorbed complexes.…”

Section: Aim Analysis Of Gas Adsorbed Complexesmentioning

confidence: 95%

Probing the bent bonds in cyclopropane systems for gas storage and separation process: A computational study

Wakchaure

Ganguly

2020

J Comput Chem

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The hydrogen, carbon dioxide, and carbon monoxide gas adsorption and storage capacity of lithium‐decorated cyclopropane ring systems were examined with quantum chemical calculations at density functional theory, DFT M06‐2X functional using 6‐31G(d) and cc‐pVDZ basis sets. To examine the reliability of M06‐2X DFT functional, a few representative systems are also examined with complete basis set CBS‐QB3 method and CCSD‐aug‐cc‐pVTZ level of theory. The cyclopropane systems can bind to one Li+ ion; however, the corresponding the methylated systems can bind with two Li+ ions. The cyclopropane systems can adsorb six hydrogen molecules with an average binding energy of 3.8 kcal/mol. The binding free energy (ΔG) values suggest that the hydrogen adsorption process is feasible at 273.15 K. The calculation of desorption energies indicates the recyclable property of gas adsorbed complexes. The same number of CO2 and CO gas molecules can also be adsorbed with an average binding energy of −14.4 kcal/mol and −10.7 kcal/mol, respectively. The carbon dioxide showed ~3–4 kcal/mol better binding energy as compared to carbon monoxide and hence such designed systems can function as a potential candidate for the separation of these flue gas molecules. The nature of interactions in complexes was examined with atoms in molecules analysis revealed the electrostatic nature for the interaction of Li+ ion with cyclopropane rings. The chemical hardness and electrophilicity calculations showed that the gas adsorbed complexes are rigid and therefore robust as gas storage materials.

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“…B3LYP is one of the more popular DFT methods for structures of organic molecules due to the reasonably good compromise between accuracy and speed . Recent publications have shown that the M06‐2X method performs well in a number of property evaluations . It is a popular hybrid meta exchange‐correlation functional DFT method and was applied here with the 6‐311 + g(2d,p) basis set .…”

Section: Methodsmentioning

confidence: 99%

Structural and thermochemical properties of methyl ethyl sulfide alcohols: HOCH₂SCH₂CH₃, CH₃SCH(OH)CH₃, CH₃SCH₂CH₂OH, and radicals corresponding to loss of H atom

Song

Bozzelli

2018

J of Physical Organic Chem

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Sulfide alkoxy radicals are important intermediates during the partial oxidation of alkyl sulfides in atmospheric chemistry and in combustion. The atmospheric reaction sequence to formation of the alkoxy radicals includes (1) initial reaction with OH to create a radical on a carbon site, (2) the carbon radical then associates with 3 O 2 to form a peroxy radical, and (3) an NO radical reacts with the peroxy radical to form an alkoxy radical (RO•) plus NO 2 . This study determines structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (Δ f H°, S°, and C p (T)) of 3 corresponding alcohols HOCH 2 SCH 2 CH 3 , CH 3 SCH(OH)CH 3 , and CH 3 SCH 2 CH 2 OH of methyl ethyl sulfides studied in order to characterize the thermochemistry of the respective alkoxy radicals. The lowest energy molecular structures were calculated using the B3LYP density functional level of theory with the 6-311G(2d,d,p) basis set. Standard enthalpies of formation (Δ f H°2 98 ) for the radicals and their parent molecules were calculated using B3LYP/6-31 + G(2d,p), CBS-QB3, M062x/6-311 + g(2d,p), and G3MP2B3 methods. Isodesmic reactions were used to determine Δ f H°values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6-31 + G(d,p) level theory. The contributions for S°2 98 and C p (T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by CBS-QB3 calculations, with contributions from torsion frequencies replaced by internal rotor contributions. Group additivity and hydrogen bond increment values were developed for estimating properties of structurally similar and larger sulfur-containing peroxide molecules and their radicals.

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The origin and magnitude of intramolecular quasi-cyclic S⋯O and S⋯S interactions revisited: A computational study

Cited by 25 publications

References 43 publications

Rational Design of Mono- and Dianions as Superacids Through π-Hole Interaction: Implications for Lithium and Magnesium Ion Batteries

Rational Design of Mono- and Dianions as Superacids Through π-Hole Interaction: Implications for Lithium and Magnesium Ion Batteries

Probing the bent bonds in cyclopropane systems for gas storage and separation process: A computational study

Structural and thermochemical properties of methyl ethyl sulfide alcohols: HOCH₂SCH₂CH₃, CH₃SCH(OH)CH₃, CH₃SCH₂CH₂OH, and radicals corresponding to loss of H atom

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The origin and magnitude of intramolecular quasi-cyclic S⋯O and S⋯S interactions revisited: A computational study

Cited by 25 publications

References 43 publications

Rational Design of Mono- and Dianions as Superacids Through π-Hole Interaction: Implications for Lithium and Magnesium Ion Batteries

Rational Design of Mono- and Dianions as Superacids Through π-Hole Interaction: Implications for Lithium and Magnesium Ion Batteries

Probing the bent bonds in cyclopropane systems for gas storage and separation process: A computational study

Structural and thermochemical properties of methyl ethyl sulfide alcohols: HOCH2SCH2CH3, CH3SCH(OH)CH3, CH3SCH2CH2OH, and radicals corresponding to loss of H atom

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Structural and thermochemical properties of methyl ethyl sulfide alcohols: HOCH₂SCH₂CH₃, CH₃SCH(OH)CH₃, CH₃SCH₂CH₂OH, and radicals corresponding to loss of H atom