Probing ground and low-lying excited states for HIO2 isomers

Souza, Gabriel L. C. de; Brown, Alex

doi:10.1063/1.4903789

Cited by 9 publications

(12 citation statements)

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“…To the best of our knowledge, there is no experimental data for (HIO 2 ) isomers in the gas phase. Theoretical wavenumbers from the recent works of Grant et al 16 and Souza et al 17 are in good agreement with our computed values (see Table 1). Differences between our computed vibrational frequencies and their literature counterparts are less than 10%.…”

Section: Resultssupporting

confidence: 90%

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Thermochemistry of HIO₂ Species and Reactivity of Iodous Acid with OH Radical: A Computational Study

Khanniche

Louis

Cantrel

et al. 2017

ACS Earth Space Chem.

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This paper reports computations of thermochemical properties [Δf H 298 K °, S 298 K °, and C p = f(T)] of HIO2 isomers (HOOI and HOIO) together with the kinetic parameters of the gas-phase HOIO + OH reaction. The calculations are performed using the CCSD(T) method on structures previously optimized at the B3LYP/aug-cc-pVTZ level of theory. Spin–orbit coupling is computed by employing the CASSCF/CASPT2/RASSI scheme. The standard enthalpies of formation at 298 K are equal to −24.8 ± 0.9 and 18.7 ± 0.4 kJ mol–1 for HOIO and HOOI, respectively. The H- and O(H)-abstraction pathways are considered for the reaction of iodous acid (HOIO) with OH. Our calculations reveal that the H-abstraction channel was exergonic by −135 kJ mol–1 at 298 K. The rate constants were computed as a function of the temperature (250–2500 K) using classical and variational transition state theory. At the CCSD(T)/CBS level, the rate constants are (in cm3 molecule–1 s–1): k Habs(T) = 2.22 × 10–19 T 1.83 exp[−4.9 (kJ mol–1)/RT] and k OHabs(T) = 7.73 × 10–21 T 2.66 exp[−70.2 (kJ mol–1)/RT]. The HOIO + OH overall reaction is significantly dominated by the HOIO + OH → OIO + H2O channel for tropospheric temperatures. The atmospheric lifetime of HOIO is estimated to be approximately 64 years. Thermochemical properties and kinetic parameters derived from this study can be used as input parameters in chemistry-transport models, for which iodine is important in the case of radioactive airbone species released for a severe accident occurring to nuclear power plants.

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Section: Resultssupporting

confidence: 90%

“…Our structures agree well with those from previous work. 14,17 The value for SOC is more important for HOOI (−5.1 kJ mol −1 ), which contains monovalent iodine, than that for the HOIO isomer, in which I is divalent (−2.9 kJ mol −1 ).…”

Section: Resultsmentioning

confidence: 99%

Thermochemistry of HIO₂ Species and Reactivity of Iodous Acid with OH Radical: A Computational Study

Khanniche

Louis

Cantrel

et al. 2017

ACS Earth Space Chem.

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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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“…[HOIO] was about 2 × 10 6 molecules cm –3 . Previous computational studies ,− have been mainly performed to determine the structural and thermochemical properties [Δ f H 298K ° , S 298K ° , and C p = f ( T )] of gas-phase HIO 2 isomers (HOIO, HOOI, and HIOO). HOIO was the most stable isomer in terms of standard enthalpy of formation at 298 K .…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Tropospheric Microhydration Processes of Iodous Acid HOIO

Taamalli

Khiri

Suliman

et al. 2019

ACS Earth Space Chem.

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The microhydration of iodous acid has been theoretically studied using the ωB97X-D/aug-cc-pVTZ level of theory. Two hydration processes have been examined considering the addition of either successive water molecules or water clusters with a number of water molecules from 1 to 4. The singlet potential energy surface exploration revealed four monohydrates, seven dihydrates, nine trihydrates, and ten tetrahydrates. The thermodynamic properties of the hydration reactions have been calculated at different levels of theory including density functional theory and coupled cluster calculations DK-CCSD(T) with the ANO-RCC-VQZP basis sets. Standard reaction enthalpy and standard Gibbs free reaction energy were computed. The temperature dependence of Δr G°(T) was evaluated for all studied aggregates over the temperature range of 200–400 K. The results showed that the hydrated forms of HOIO can exist in tropospheric conditions. Atmospheric implications in terms of assessing the molecular concentrations of HOIO and water aggregates are discussed.

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Probing ground and low-lying excited states for HIO2 isomers

Cited by 9 publications

References 50 publications

Thermochemistry of HIO₂ Species and Reactivity of Iodous Acid with OH Radical: A Computational Study

Thermochemistry of HIO₂ Species and Reactivity of Iodous Acid with OH Radical: A Computational Study

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

Unraveling the Tropospheric Microhydration Processes of Iodous Acid HOIO

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Probing ground and low-lying excited states for HIO2 isomers

Cited by 9 publications

References 50 publications

Thermochemistry of HIO2 Species and Reactivity of Iodous Acid with OH Radical: A Computational Study

Thermochemistry of HIO2 Species and Reactivity of Iodous Acid with OH Radical: A Computational Study

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

Unraveling the Tropospheric Microhydration Processes of Iodous Acid HOIO

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Thermochemistry of HIO₂ Species and Reactivity of Iodous Acid with OH Radical: A Computational Study

Thermochemistry of HIO₂ Species and Reactivity of Iodous Acid with OH Radical: A Computational Study