Investigation of the Reaction Mechanism and Kinetics of Iodic Acid with OH Radical Using Quantum Chemistry

Khanniche, Sarah; Louis, Florent; Cantrel, Laurent; Černušák, Ivan

doi:10.1021/acsearthspacechem.7b00038

Cited by 12 publications

(11 citation statements)

References 57 publications

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“…They also play a role as oxidants in many pathophysiological processes and have antibacterial properties [48][49][50]. In addition, halogen oxoacids, such as HXO 2 [51][52][53][54] and HXO 3 [55][56][57] (X = Cl, Br, I), have been proposed as key intermediates in elementary reactions to decompose ozone.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Bond versus Halogen Bond in HXOn (X = F, Cl, Br, and I) Complexes with Lewis Bases

Quiñonero

Frontera

2019

Inorganics

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We have theoretically studied the formation of hydrogen-bonded (HB) and halogen-bonded (XB) complexes of halogen oxoacids (HXO n ) with Lewis bases (NH 3 and Cl − ) at the CCSD(T)/CBS//RIMP2/aug-cc-pVTZ level of theory. Minima structures have been found for all HB and XB systems. Proton transfer is generally observed in complexes with three or four oxygen atoms, namely, HXO 4 :NH 3 , HClO 3 :Cl − , HBrO 3 :Cl − , and HXO 4 :Cl − . All XB complexes fall into the category of halogen-shared complexes, except for HClO 4 :NH 3 and HClO 4 :Cl − , which are traditional ones. The interaction energies generally increase with the number of O atoms. Comparison of the energetics of the complexes indicates that the only XB complexes that are more favored than those of HB are HIO:NH 3 , HIO:Cl − , HIO 2 :Cl − , and HIO 3 :Cl − . The atoms-in-molecules (AIM) theory is used to analyze the complexes and results in good correlations between electron density and its Laplacian values with intermolecular equilibrium distances. The natural bon orbital (NBO) is used to analyze the complexes in terms of charge-transfer energy contributions, which usually increase as the number of O atoms increases. The nature of the interactions has been analyzed using the symmetry-adapted perturbation theory (SAPT) method. The results indicate that the most important energy contribution comes from electrostatics, followed by induction.

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Section: Introductionmentioning

confidence: 99%

Hydrogen Bond versus Halogen Bond in HXOn (X = F, Cl, Br, and I) Complexes with Lewis Bases

Quiñonero

Frontera

2019

Inorganics

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“…Computational chemistry techniques have been used as a complementary approach to laboratory studies in predicting PAH-TP formations. − Density-functional theory (DFT) has previously been applied to a number of atmospheric speciation studies. ,− Results of these computational studies have not only elucidated elementary steps , but often predict which PAH-TP is favored when many potential PAH-TP product isomers are possible. Furthermore, computational chemistry can be extended for suspect screening analysis.…”

Section: Introductionmentioning

confidence: 99%

Evaluating Computational and Structural Approaches to Predict Transformation Products of Polycyclic Aromatic Hydrocarbons

Titaley

Walden

Dorn

et al. 2018

Environ. Sci. Technol.

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Polycyclic aromatic hydrocarbons (PAHs) undergo transformation reactions with atmospheric photochemical oxidants, such as hydroxyl radicals (OH•), nitrogen oxides (NOx), and ozone (O 3 ). The most common PAH-transformation products (PAH-TPs) are nitrated-, oxygenated-, and hydroxylated-PAHs (NPAHs, OPAHs, and OHPAHs, respectively), some of which are known to pose potential human health concerns. We sampled four theoretical approaches for predicting the location of reactive sites on PAHs (i.e., the carbon where atmospheric oxidants attack), and hence the chemoselectivity of the PAHs. All computed results are based on Density Functional Theory (B3LYP/6-31G(d) optimized structures and energies). The four approaches are: 1) Clar's prediction of aromatic resonance structures, 2) thermodynamic stability of all OHPAH adduct intermediates, 3) computed atomic charges (Natural Bond order, ChelpG, and Mulliken) at each carbon on the PAH, and 4) average local ionization energy (ALIE) at atom or bond sites. To evaluate the accuracy of these approaches, the predicted PAH-TPs were compared to published laboratory observations of major NPAH, OPAH, and OHPAH products in both gas-and particlephases. We found that the Clar's resonance structures were able to predict the least stable rings on the PAHs but did not offer insights in terms of which individual carbon is most reactive. The OHPAH adduct thermodynamics and the ALIE approaches were the most accurate when *

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“…is endothermic by 25 kJ mol −1 (14 kJ mol −1 according to previous work at a higher level of theory; Khanniche et al, 2017b) and so most likely does not occur. However, the reaction…”

Section: Photolysis Productsmentioning

confidence: 78%

Determination of the absorption cross sections of higher-order iodine oxides at 355 and 532 nm

et al. 2020

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Abstract. Iodine oxides (IxOy) play an important role in the atmospheric chemistry of iodine. They are initiators of new particle formation events in the coastal and polar boundary layers and act as iodine reservoirs in tropospheric ozone-depleting chemical cycles. Despite the importance of the aforementioned processes, the photochemistry of these molecules has not been studied in detail previously. Here, we report the first determination of the absorption cross sections of IxOy, x=2, 3, 5, y=1–12 at λ=355 nm by combining pulsed laser photolysis of I2∕O3 gas mixtures in air with time-resolved photo-ionization time-of-flight mass spectrometry, using NO2 actinometry for signal calibration. The oxides selected for absorption cross-section determinations are those presenting the strongest signals in the mass spectra, where signals containing four iodine atoms are absent. The method is validated by measuring the absorption cross section of IO at 355 nm, σ355nm,IO= (1.2±0.1) ×10-18 cm2, which is found to be in good agreement with the most recent literature. The results obtained are σ355nm,I2O3<5×10-19 cm2 molec.−1, σ355nm,I2O4= (3.9±1.2)×10-18 cm2 molec.−1, σ355nm,I3O6= (6.1±1.6)×10-18 cm2 molec.−1, σ355nm,I3O7= (5.3±1.4)×10-18 cm2 molec.−1, and σ355nm,I5O12= (9.8±1.0)×10-18 cm2 molec.−1. Photodepletion at λ=532 nm was only observed for OIO, which enabled determination of upper limits for the absorption cross sections of IxOy at 532 nm using OIO as an actinometer. These measurements are supplemented with ab initio calculations of electronic spectra in order to estimate atmospheric photolysis rates J(IxOy). Our results confirm a high J(IxOy) scenario where IxOy is efficiently removed during daytime, implying enhanced iodine-driven ozone depletion and hindering iodine particle formation. Possible I2O3 and I2O4 photolysis products are discussed, including IO3, which may be a precursor to iodic acid (HIO3) in the presence of HO2.

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Investigation of the Reaction Mechanism and Kinetics of Iodic Acid with OH Radical Using Quantum Chemistry

Cited by 12 publications

References 57 publications

Hydrogen Bond versus Halogen Bond in HXOn (X = F, Cl, Br, and I) Complexes with Lewis Bases

Hydrogen Bond versus Halogen Bond in HXOn (X = F, Cl, Br, and I) Complexes with Lewis Bases

Evaluating Computational and Structural Approaches to Predict Transformation Products of Polycyclic Aromatic Hydrocarbons

Determination of the absorption cross sections of higher-order iodine oxides at 355 and 532 nm

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