Quantum chemical investigation of the reaction of O(3 P 2) with certain hydrocarbon radicals

Gupta, Ashutosh; Singh, Rakesh; Singh, V. B.; Mishra, Brijesh Kumar; Sathyamurthy, N.

doi:10.1007/s12039-007-0059-8

Cited by 9 publications

(11 citation statements)

References 14 publications

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“…[42] Several groups have independently performed ab initio calculations of some of the reaction channels of O( 3 P) + (CH 3 ) 2 CH. [43][44][45] However, the heats of formation and reaction enthalpies estimated here agree well with previously reported experimental values, with an accuracy of 1.8 kcal mol À1 .…”

Section: Methodssupporting

confidence: 90%

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

2012

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This paper reports on the gas-phase radical-radical dynamics of the reaction of ground-state atomic oxygen [O((3)P), from the photodissociation of NO(2)] with secondary isopropyl radicals [(CH(3))(2)CH, from the supersonic flash pyrolysis of isopropyl bromide]. The major reaction channel, O((3)P)+(CH(3))(2)CH→C(3)H(6) (propene)+OH, is examined by high-resolution laser-induced fluorescence spectroscopy in crossed-beam configuration. Population analysis shows bimodal nascent rotational distributions of OH (X(2)Π) products with low- and high-N'' components in a ratio of 1.25:1. No significant spin-orbit or Λ-doublet propensities are exhibited in the ground vibrational state. Ab initio computations at the CBS-QB3 theory level and comparison with prior theory show that the statistical method is not suitable for describing the main reaction channel at the molecular level. Two competing mechanisms are predicted to exist on the lowest doublet potential-energy surface: direct abstraction, giving the dominant low-N'' components, and formation of short-lived addition complexes that result in hot rotational distributions, giving the high-N'' components. The observed competing mechanisms contrast with previous bulk kinetic experiments conducted in a fast-flow system with photoionization mass spectrometry, which suggested a single abstraction pathway. In addition, comparison of the reactions of O((3)P) with primary and tertiary hydrocarbon radicals allows molecular-level discussion of the reactivity and mechanism of the title reaction.

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Section: Methodssupporting

confidence: 90%

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

2012

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“…typified with a square planar geometry around Cu(II) ions . In the contrary, the electronic spectrum of [Cu 2 (HL) 2 (H 2 O) 2 (ClO 4 ) 2 ].8H 2 O complex (4) displays two medium absorption bands at 681 and 576 nm, due to 2 B 1g → 2 B 2g and 2 B 1g → 2 E g transitions, respectively, attributed to a distorted octahedral geometry around Cu(II) ions . The magnetic moment value of Cu(II) complex (4) (1.61 B.M.)…”

Section: Resultsmentioning

confidence: 99%

Molecular modeling, spectral investigation and thermal studies of the new asymmetric Schiff base ligand; (E)‐N'‐(1‐(4‐((E)‐2‐hydroxybenzylideneamino)phenyl)ethylidene)morpholine‐4‐carbothiohydrazide and its metal complexes: Evaluation of their antibacterial and anti‐molluscicidal activity

El-Samanody

Abouel‐Enein

Emara

2018

Applied Organom Chemis

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A new tetradentate asymmetric Schiff base ligand; (E)-N'-(1-(4-((E)-2hydroxybenzylideneamino)phenyl)ethylidene)morpholine-4-carbothiohydrazide (H 2 L) was prepared by consecutive condensation reactions between p-aminoacetophenone, salicylaldehyde and 4-morpholinethiosemicarbazide. The structures of the obtained ligand along with its Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Cr(III), Fe(III) and Ru(III) complexes were authenticated by different analytical and spectral techniques. The ligand behaves as a monobasic tetradentate one and chelates with metal ions through the deprotonated phenolic oxygen, imine nitrogen, thione sulfur and azomethine nitrogen atoms (ONNS chromophore). All nonelectrolyte metal complexes possess octahedral geometry, except Ni(II) and Cu(II) complexes (2, 3) which have tetra-coordinate structures. The thermal stability of metal complexes is higher than that of the free ligand and the general thermal degradation pathways were discussed based on thermogravimetric technique. The activation thermodynamic parameters as well as the order of reaction (n) were estimated from DTG curves by using Piloyan method. Thermogravimetric analyses and mass spectra of metal complexes confirm the number of solvents in their inner and outer spheres.Molecular modeling data were used to demonstrate the thermal decomposition pathways of the ligand and its metal complexes, confirming their chemical structures. The ESR spectra of Cu(II) complexes indicate that the unpaired electron is localized mainly in the d (x 2 -y 2 ) orbital with axial symmetry. Powder X-ray diffraction analyses for Co(II), Cu(II) and Ru(III) complexes (1,3,7) show that copper complex has a crystalline nature, whereas, cobalt and ruthenium complexes are amorphous. The ligand and its metal complexes were tested in vitro for their anti-molluscicidal activity against Eobania vermiculata. The results reveal that the investigated compounds have remarkable antimolluscicidal activities against the tested land snail with various sensitivity levels. The synthesized compounds were also screened in vitro for their

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“…23 In addition, ab initio calculations have been performed by several theoretical groups, including the present authors, to examine various reaction channels of O( 3 P) + C 2 H 5 . 15,24,25 No gas-phase dynamics study of the reactive scattering process: O( 3 P) + C 2 H 5 → H( 2 S) + C 2 H 4 O has been reported to the best of our knowledge. Herein, the translational energy distributions of the nascent H-atom products are examined using tunable VUV-LIF spectroscopy in the Lyman-α region.…”

Section: Introductionmentioning

confidence: 99%

A Gas-Phase Investigation of Oxygen-Hydrogen Exchange Reaction of O(³P) + C₂H₅→ H(²S) + C₂H₄O

Jang¹,

Park²,

Choi³

2014

Bulletin of the Korean Chemical Society

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The gas-phase radical-radical reaction O( 3 P) + C 2 H 5 (ethyl) → H( 2 S) + CH 3 CHO (acetaldehyde) was investigated by applying a combination of vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed beam configuration and ab initio calculations. The two radical reactants O( 3 P) and C 2 H 5 were respectively produced by photolysis of NO 2 and supersonic flash pyrolysis of the synthesized precursor azoethane. Doppler profile analysis of the nascent H-atom products in the Lyman-α region revealed that the average translational energy of the products and the average fraction of the total available energy released as translational energy were 5.01 ± 0.72 kcal mol −1 and 6.1%, respectively. The empirical data combined with CBS-QB3 level ab initio theory and statistical calculations demonstrated that the title exchange reaction is a major channel and proceeds via an addition-elimination mechanism through the formation of a short-lived, dynamical addition complex on the doublet potential energy surface. On the basis of systematic comparison with several exchange reactions of hydrocarbon radicals, the observed small kinetic energy release can be explained in terms of the loose transition state with a product-like geometry and a small reverse activation barrier along the reaction coordinate.

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Quantum chemical investigation of the reaction of O(3 P 2) with certain hydrocarbon radicals

Cited by 9 publications

References 14 publications

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

A Gas-Phase Investigation of Oxygen-Hydrogen Exchange Reaction of O(³P) + C₂H₅→ H(²S) + C₂H₄O

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Quantum chemical investigation of the reaction of O(3 P 2) with certain hydrocarbon radicals

Cited by 9 publications

References 14 publications

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(3P)+(CH3)2CH→C3H6+OH

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(3P)+(CH3)2CH→C3H6+OH

A Gas-Phase Investigation of Oxygen-Hydrogen Exchange Reaction of O(3P) + C2H5→ H(2S) + C2H4O

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Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

A Gas-Phase Investigation of Oxygen-Hydrogen Exchange Reaction of O(³P) + C₂H₅→ H(²S) + C₂H₄O