Atmospheric fate of formyl chloride and mechanisms of the gas-phase reactions with OH radicals and Cl atoms

Vijayakumar, S.; Wilmouth, D. M.

doi:10.1016/j.cplett.2021.138709

Cited by 3 publications

(4 citation statements)

References 25 publications

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“…To obtain more accurate values, energies were optimized at different levels of theory and basis sets, such as M062X and MP2, in combination with 6-31G(d,p), 6-31+G(d,p), cc-pVTZ, cc-pVDZ, aug-cc-pVTZ, and aug-cc-pV(T+d)Z. To verify that the transition states are connected to the reactants and products, IRC (intrinsic reaction coordinate) calculations were performed at the M062X level of theory. The vibrational frequency scaling factor 0.963 was used for the M062X/aug-cc-pV(T+d)Z level of theory .…”

Section: Methodsmentioning

confidence: 99%

“…MRCI+Q in combination with aug-ano-pVTZ and ZORA (zeroth-order regular approximation) was used for refining energies. Density functional theory (DFT) and single- and multireference correlation methods can be executed using ORCA, which is one of the most versatile quantum chemistry packages available. , Among all of the above theories, the energy values obtained at CCSD(T)/aug-cc-pV(T+d)Z//M062X/aug-cc-pV(T+d)Z for reactions – and QCISD(T)/aug-cc-pV(T+d)Z//M062X/aug-cc-pV(T+d)Z for reaction were used to compute the rate coefficients presented here. These rate coefficients are closer to the reported experimental values in the literature than the rate coefficients calculated from energy values obtained at our other tested levels of theory.…”

Section: Methodsmentioning

confidence: 99%

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Kinetics of the Reactions of Chlorinated Very Short-Lived Substances (VSLSs) with Chlorine Atoms

Vijayakumar,

Wilmouth

2023

J. Phys. Chem. A

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Chlorinated very short-lived substances (VSLSs), which are not controlled by the Montreal Protocol, are of current concern with regard to recovery of stratospheric ozone. Further study is needed on the temperature dependences of chlorinated VSLSs relevant to atmospheric conditions. Here, the kinetics of chlorinated VSLSs, such as chloroform (CHCl 3 ), dichloromethane (CH 2 Cl 2 ), dichloroethane (CH 2 ClCH 2 Cl), and trichloroethene (C 2 HCl 3 ) reacting with chlorine atoms, were investigated between 180 and 400 K, expanding the range of temperatures relative to previous studies. RRKM/Master Equation and Canonical Variational Transition State Theory were utilized to calculate the rate coefficients using the MultiWell suite of programs. CCSD(T), QCISD-(T), and M062X with aug-cc-pV(T+d)Z levels of theory were used to calculate the kinetic parameters. Arrhenius equations obtained from fits to the calculated rate coefficients are, and k 4 = (9.17 ± 1.8) × 10 −12 exp [(612 ± 101)/T] cm 3 molecule −1 s −1 for the reactions of CHCl 3 , CH 2 Cl 2 , CH 2 ClCH 2 Cl, and C 2 HCl 3 with Cl atoms, respectively. The rate coefficients for the reactions of chlorinated VSLSs with Cl atoms from this study are compared with the most recent recommended values from the NASA/JPL and IUPAC evaluations and with literature values. The reactivity trends of the reactions are discussed.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Kinetics of the Reactions of Chlorinated Very Short-Lived Substances (VSLSs) with Chlorine Atoms

Vijayakumar,

Wilmouth

2023

J. Phys. Chem. A

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“…The temperature-dependent rate coefficients for the reactions of halogen atoms with O 3 were calculated with CVT/SCT using the POLYRATE 2016A program and GAUSS-RATE [62,63]. The POLYRATE program is a well-known software package for calculating kinetics parameters for gas-phase reactions; a detailed procedure was given in our previous articles [64,65]. To get the canonical variational transition state rate coefficient, the generalized rate coefficients can be minimized by varying the transition state dividing surface along the reaction coordinate using the following expressions: occurring in the stratosphere, with theoretical calculations in particular providing valuable mechanistic insight.…”

Section: Kineticsmentioning

confidence: 99%

“…S1The temperature-dependent rate coefficients for the react with O3 were calculated with CVT/SCT using the POLYRATE GAUSSRATE [62,63]. The POLYRATE program is a well-known calculating kinetics parameters for gas-phase reactions; a detailed our previous articles [64,65]. To get the canonical variationa coefficient, the generalized rate coefficients can be minimized by state dividing surface along the reaction coordinate using the follo / ( ) = Ƙ / ( ) ( )…”

Section: Kineticsmentioning

confidence: 99%

Kinetics of the Reactions of Ozone with Halogen Atoms in the Stratosphere

2021

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It is well established that reaction cycles involving inorganic halogens contribute to the depletion of ozone in the atmosphere. Here, the kinetics of O3 with halogen atoms (Cl, Br, and I) were investigated between 180 and 400 K, expanding the temperature range relative to prior studies. Canonical variational transition state theory including small curvature tunneling correction (CVT/SCT) were considered, following the construction of the potential energy surfaces. MRCI + Q/aug-ano-pVTZ//MP2/aug-cc-pV(T + d)Z and MRCI + Q/aug-ano-RCC-VTZP//MP2/aug-cc-pV(T + d)Z levels of theory were used to calculate the kinetic parameters. Calculated rate coefficients were used to fit the Arrhenius equations, which are obtained to be k1 = (3.48 ± 0.4) × 10−11 exp[(−301 ± 64)/T] cm3 molecule−1 s−1, k2 = (3.54 ± 0.2) × 10−11 exp[(−990 ± 35)/T] cm3 molecule−1 s−1 and k3 = (1.47 ± 0.1) × 10−11 exp[(−720 ± 42)/T] cm3 molecule−1 s−1 for the reactions of O3 with Cl, Br, and I atoms, respectively. The obtained rate coefficients for the reactions of O3 with halogen atoms using CVT/SCT are compared to the latest recommended rate coefficients by the NASA/JPL and IUPAC evaluations. The reactivity trends and pathways of these reactions are discussed.

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Atmospheric degradation of chloroacetoacetates by Cl atoms: Reactivity, products and mechanism in coastal and industrialized areas

Straccia C,

Lugo,

Rivela

et al. 2023

Atmospheric Environment

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Atmospheric fate of formyl chloride and mechanisms of the gas-phase reactions with OH radicals and Cl atoms

Cited by 3 publications

References 25 publications

Kinetics of the Reactions of Chlorinated Very Short-Lived Substances (VSLSs) with Chlorine Atoms

Kinetics of the Reactions of Chlorinated Very Short-Lived Substances (VSLSs) with Chlorine Atoms

Kinetics of the Reactions of Ozone with Halogen Atoms in the Stratosphere

Atmospheric degradation of chloroacetoacetates by Cl atoms: Reactivity, products and mechanism in coastal and industrialized areas

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