Complexes of criegee intermediate CH2OO with CO, CO2, H2O, SO2, NO2, CH3OH, HCOOH and CH3CH3CO molecules – A DFT study on bonding, energetics and spectra

Shyama, Muraledharan; Cheviri, Meera; Priya, Angappan Mano; Lakshmipathi, Senthilkumar

doi:10.1016/j.comptc.2021.113341

Cited by 6 publications

(3 citation statements)

References 61 publications

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“…There have been numerous prior theoretical studies on the reactions of sCIs with SO 2 , ,,− most of which have primarily focused on the reactions of CH 2 OO and/or (CH 3 ) 2 COO, although some have also considered the reaction with larger CIs. ,, The potential energy surfaces were generally explored with CCSD(T)-based evaluations at stationary points or minimum energy paths determined by density functional theory. These prior studies uniformly conclude that the initial addition process between the sCI and SO 2 is strongly attractive.…”

Section: Results and Discussionmentioning

confidence: 99%

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO₂

Zou,

Liu,

Vansco

et al. 2023

J. Phys. Chem. A

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Methyl-ethyl-substituted Criegee intermediate (MECI) is a four-carbon carbonyl oxide that is formed in the ozonolysis of some asymmetric alkenes. MECI is structurally similar to the isoprene-derived methyl vinyl ketone oxide (MVK-oxide) but lacks resonance stabilization, making it a promising candidate to help us unravel the effects of size, structure, and resonance stabilization that influence the reactivity of atmospherically important, highly functionalized Criegee intermediates. We present experimental and theoretical results from the first bimolecular study of MECI in its reaction with SO 2 , a reaction that shows significant sensitivity to the Criegee intermediate structure. Using multiplexed photoionization mass spectrometry, we obtain a rate coefficient of (1.3 ± 0.3) × 10 −10 cm 3 s −1 (95% confidence limits, 298 K, 10 Torr) and demonstrate the formation of SO 3 under our experimental conditions. Through high-level theory, we explore the effect of Criegee intermediate structure on the minimum energy pathways for their reactions with SO 2 and obtain modified Arrhenius fits to our predictions for the reaction of both syn and anti conformers of MECI with SO 2 (k syn = 4.42 × 10 11 T −7.80 exp(−1401/T) cm 3 s −1 and k anti = 1.26 × 10 11 T −7.55 exp(−1397/T) cm 3 s −1 ). Our experimental and theoretical rate coefficients (which are in reasonable agreement at 298 K) show that the reaction of MECI with SO 2 is significantly faster than MVKoxide + SO 2 , demonstrating the substantial effect of resonance stabilization on Criegee intermediate reactivity.

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Section: Results and Discussionmentioning

confidence: 99%

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO₂

Zou,

Liu,

Vansco

et al. 2023

J. Phys. Chem. A

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“…Atoms in molecules (AIM) [26,27] and natural bond population [28][29][30] studies were performed to comprehend the nature of bonds and the charge transfer process. To gain a better understanding, we expand the investigation into a solvent medium (water) using the PCM [31]model.…”

Section: Computational Detailsmentioning

confidence: 99%

Iodine Coadsorbed OH-Copper Phthalocyanine for Dopamine Sensing – A DFT Study

Sangeetha,

Lakshmipathi

2024

Preprint

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Density Functional Theory (DFT) was employed to investigate the sensing behavior of the neurotransmitter dopamine (DA) when interacting with OH-functionalized copper phthalocyanines (CuPCs) and copper phthalocyanines coadsorbed with iodine (CuIPc), both in gaseous and aqueous media. The study revealed that CuIPc demonstrates a superior capacity for detecting dopamine molecules compared to CuPc. Within these complexes, hydrogen bonds and coordination bonds were observed, with hydrogen bonds playing a pivotal role in the dopamine adsorption process. The enhanced electrical conductivity of CuPc sheets after iodine adsorption, along with the high adsorption energy of the iodine-coadsorbed CuPc/DA complexes, underscores the significance of iodine in this context. It is noteworthy that the utilization of iodine significantly enhances the sensing response for dopamine. In summary, copper phthalocyanine coadsorbed with iodine emerges as a promising material for dopamine sensors, offering possibilities for further advancements in this field.

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“…Atoms in molecules (AIM) analysis is a reliable tool to determine the nature of hydrogen bonds in a structure [36][37][38].…”

Section: Aim Analysismentioning

confidence: 99%

Intramolecular interactions (O-H∙∙∙O, C-H∙∙∙N, N-H∙∙∙π) in isomers of neutral, cation, and anion dopamine molecules: A DFT study on the influence of solvents (water and ethanol)

Sangeetha

Lakshmipathi

2023

J Mol Model

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The investigation reports the intramolecular interactions present in the isomers of neutral (DA 0 ), anionic (DA -), and cationic (DA + ) dopamine isomers in gas, water, and ethanol mediums. Isomers of Cation dopamine show no intramolecular interactions in the solvent. Neutral and anion isomers have O-H•••O, C-H•••N hydrogen bonds and N-H π interactions. All the interactions are electrostatic in nature. In solvents, intramolecular interactions are elongated and thereby weakened. Natural charges from NBO analysis show that O-H•••O bonds and the N-H•••π interactions are the most and least polar, respectively, among all the three interactions. 1 H NMR study reveals the inverse linear correlation between shielding constant and electron density in a solvent medium. Homo-Lumo energy gap indicates higher stability for neutral and cationic forms of dopamine isomers in water and ethanol medium.

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Complexes of criegee intermediate CH2OO with CO, CO2, H2O, SO2, NO2, CH3OH, HCOOH and CH3CH3CO molecules – A DFT study on bonding, energetics and spectra

Cited by 6 publications

References 61 publications

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO₂

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO₂

Iodine Coadsorbed OH-Copper Phthalocyanine for Dopamine Sensing – A DFT Study

Intramolecular interactions (O-H∙∙∙O, C-H∙∙∙N, N-H∙∙∙π) in isomers of neutral, cation, and anion dopamine molecules: A DFT study on the influence of solvents (water and ethanol)

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Complexes of criegee intermediate CH2OO with CO, CO2, H2O, SO2, NO2, CH3OH, HCOOH and CH3CH3CO molecules – A DFT study on bonding, energetics and spectra

Cited by 6 publications

References 61 publications

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2

Iodine Coadsorbed OH-Copper Phthalocyanine for Dopamine Sensing – A DFT Study

Intramolecular interactions (O-H∙∙∙O, C-H∙∙∙N, N-H∙∙∙π) in isomers of neutral, cation, and anion dopamine molecules: A DFT study on the influence of solvents (water and ethanol)

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Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO₂

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO₂