Ab Initio Studies of ClO<sub><i>x</i></sub> Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

Zhu, R. S.; Lin, Ming‐Chang

doi:10.1002/cphc.200400305

Cited by 33 publications

(33 citation statements)

References 51 publications

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“…The VariFlex code developed by Klippenstein et al [39] is employed for our purpose, in the temperature range of 200-3000 K and the pressure range from 0.01 atm to 100 atm of N 2 bath gas. The energy-transfer rate coefficients were computed on the basis of the exponential down model with the DE down value of 200 cm À1 in N 2 in the work recommended by Zhu and Lin [40]. The component rates are evaluated at the E-and J-resolved levels.…”

Section: Resultsmentioning

confidence: 99%

Thermal rate constants of the pyrolysis of n-Heptane

Ding

Zhang

Han

2011

Combustion and Flame

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Section: Resultsmentioning

confidence: 99%

Thermal rate constants of the pyrolysis of n-Heptane

Ding

Zhang

Han

2011

Combustion and Flame

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“…Harmonic vibrational frequencies and the zeropoint energies (ZPE) The Cl atoms do not react with NO 2 via bimolecular processes to produce ClO + NO since the reaction is endothermic by 42.4 kJ · mol -1 . 3 Instead, the reaction of Cl atoms with NO 2 occurs via three-body association with a termolecular rate constant of 7.2 × 10 -31 cm 6 molecule -2 s -1 . 9 Under the present total pressure of 80 Pa, it is estimated that the three-body association reaction occurs slowly on a time scale of tens of milliseconds.…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

Reaction Mechanisms of C₂Cl₃ + NO₂ via Nitro and Nitrite Adducts

Liu

Xiang

et al. 2008

J. Phys. Chem. A

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The atmospherically and environmentally important reaction of chlorinated vinyl radical with nitrogen dioxide (C 2 Cl 3 + NO 2 ) is investigated by step-scan time-resolved Fourier transform infrared emission spectroscopy and electronic structure calculations. Vibrationally excited products of CO, NO, Cl 2 CO, and NO 2 are observed in the IR emission spectra. Geometries of the major intermediates and transition states along the potential energy surface are optimized at the B3LYP/6-311G(d) level, and their energies are refined at the CCSD(T)/ 6-311+G(d) level. The reaction mechanisms are characterized to be barrierless addition-elimination via nitro (C 2 Cl 3 -NO 2 ) and nitrite (C 2 Cl 3 -ONO) adducts. Four energetically accessible reaction routes are revealed, i.e., the decomposition of the nitrite adduct forming C 2 Cl 3 O + NO and its sequential dissociation to CO + NO + CCl 3 , the elimination of ClNO from the nitrite adduct leading to ClNO + Cl 2 CCO, the Cl-atom shift of the nitrite adduct followed by the decomposition to CCl 3 CO + NO, and the O-atom shift of the nitro adduct followed by C-C bond cleavage forming ClCNO + Cl 2 CO. In competition with these reactive fluxes, the back-decomposition of nitro or nitrite adducts leads to the prompt formation of vibrationally excited NO 2 and the long-lived reaction adducts facilitate the vibrational energy transfer. Moreover, the product channels and mechanisms of the C 2 Cl 3 + NO 2 reaction are compared with the C 2 H 3 + NO 2 reaction to explore the effect of chlorine substitution. It is found that the two reactions mainly differ in the initial addition preferentially by the N-attack forming nitro adducts (only N-attack is plausible for the C 2 H 3 + NO 2 reaction) or the O-attack forming nitrite adducts (O-attack is slightly more favorable and N-attack is also plausible for the C 2 Cl 3 + NO 2 reaction). The addition selectivity can be fundamentally correlated to the variation of the charge density of the end carbon atom of the double bond induced by chlorine substitution due to the electron-withdrawing effect of chlorine groups.

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“…Of its isomeric forms, namely cis-and trans-chlorine nitrite (ClONO), nitryl chloride is the most stable form, and previous ab initio studies by Lee 1, 2 and Zhu et al 3 affirm this. Both nitryl chloride and its isomers are important nitrogen reservoirs of atmospheric chlorine, and are formed by a coupling reaction of Cl atom and NO 2 .…”

Section: Introductionmentioning

confidence: 92%

An ab initio investigation of the ground and low-lying singlet and triplet electronic states of XNO2 and XONO (X = Cl, Br, and I)

Peterson

Francisco

2014

The Journal of Chemical Physics

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A systematic ab initio treatment of the nitryl halides (XNO2) and the cis- and trans- conformers of the halide nitrites (XONO), where X = Cl, Br, and I, have been carried out using highly correlated methods with sequences of correlation consistent basis sets. Equilibrium geometries and harmonic frequencies have been accurately calculated in all cases at the explicitly correlated CCSD(T)-F12b level of theory, including the effects of core-valence correlation for the former. Where experimental values are available for the equilibrium structures (ClNO2 and BrNO2), the present calculations are in excellent agreement; however, the X-O distances are slightly too long by about 0.01 Å due to missing multireference effects. Accurate predictions for the iodine species are made for the first time. The vertical electronic excitation spectra have been calculated using equation-of-motion coupled cluster methods for the low-lying singlet states and multireference configuration interaction for both singlet and triplet states. The latter also included the effects of spin-orbit coupling to provide oscillator strengths for the ground state singlet to excited triplet transitions. While for ClNO2 the transitions to excited singlet states all occur at wavelengths shorter than 310 nm, there is one longer wavelength singlet transition in BrNO2 and two in the case of INO2. The long wavelength tail in the XNO2 species is predicted to be dominated by transitions to triplet states. In addition to red-shifting from X = Cl to I, the triplet transitions also increase in oscillator strength, becoming comparable to many of the singlet transitions in the case of INO2. Hence in particular, the latter species should be very photolabile. Similar trends are observed and reported for the halogen nitrites, many of which for the first time.

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Ab Initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

Cited by 33 publications

References 51 publications

Thermal rate constants of the pyrolysis of n-Heptane

Thermal rate constants of the pyrolysis of n-Heptane

Reaction Mechanisms of C₂Cl₃ + NO₂ via Nitro and Nitrite Adducts

An ab initio investigation of the ground and low-lying singlet and triplet electronic states of XNO2 and XONO (X = Cl, Br, and I)

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Ab Initio Studies of ClOx Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

Cited by 33 publications

References 51 publications

Thermal rate constants of the pyrolysis of n-Heptane

Thermal rate constants of the pyrolysis of n-Heptane

Reaction Mechanisms of C2Cl3 + NO2 via Nitro and Nitrite Adducts

An ab initio investigation of the ground and low-lying singlet and triplet electronic states of XNO2 and XONO (X = Cl, Br, and I)

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Ab Initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

Reaction Mechanisms of C₂Cl₃ + NO₂ via Nitro and Nitrite Adducts