DIRECT DYNAMICS INVESTIGATION ON MECHANISM OF REACTION BETWEEN TRICHLORIDE AND H RADICAL

Direct dynamics within the framework of DFT has been used to study the reaction between Boron trichloride and H radical. Two sets of trajectories amounting to a total of 40 were simulated for different collision sites and initial velocities. Two reactive channels have been found. One is a Cl atom abstraction channel and the other is a Cl atom elimination channel. The detailed mechanisms of both reactive channels were depicted by sampling trajectories. For the first channel, the reaction mechanism proposed by ab initio calculations was represented. For the second channel, transition state was mapped out after the dynamics simulation.

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Nitro–Nitrite Isomerization and Transition State Switching in the Dissociation of Ionized Nitromethane: A Threshold Photoelectron–Photoion Coincidence Spectroscopy Study

European Journal of Mass Spectrometry ◽

10.1255/ejms.943 ◽

2009 ◽

Vol 15 (2) ◽

pp. 157-166 ◽

Cited By ~ 6

Author(s):

Brandon Ferrier ◽

Anne-Marie Boulanger ◽

David M.P. Holland ◽

David A. Shaw ◽

Paul M. Mayer

Keyword(s):

Transition State ◽

Ab Initio Calculations ◽

Ab Initio ◽

Bond Cleavage ◽

Cleavage Reaction ◽

Nitrite Ion ◽

Methyl Nitrite ◽

Bond Cleavage Reaction ◽

Entropy Of Activation ◽

Lower Entropy

Threshold photoelectron–photoion coincidence (TPEPICO) spectroscopy has been employed to investigate the competition between bond cleavage and rearrangement reactions in the dissociation of ionized nitromethane, 1. Modeling TPEPICO breakdown diagrams with a combination of RRKM theory and ab initio calculations at the G3 level of theory allowed the derivation of the activation energy for the isomerisation of 1 to ionized methyl nitrite, 2, 82 kJ mol−1. In addition, evidence was found for a transition state switch in the bond cleavage reaction in 1 leading to CH3• + NO2+. As internal energy increases, the effective transition state for this reaction becomes tighter (i.e. is characterized by a lower entropy of activation, Δ‡S). Fitted thresholds for NO+ and CH2OHO+ ions, originating from the isomeric methyl nitrite ion, are consistent with G3 level ab initio calculations.

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Ab initio calculations concerning the reaction mechanism of the copper(II) catalyzed glycine condensation in aqueous sodium chloride solution

Chemical Physics Letters ◽

10.1016/0009-2614(92)86044-i ◽

1992 ◽

Vol 197 (1-2) ◽

pp. 181-186 ◽

Cited By ~ 24

Author(s):

Klaus R. Liedl ◽

Bernd M. Rode

Keyword(s):

Reaction Mechanism ◽

Sodium Chloride ◽

Ab Initio Calculations ◽

Ab Initio ◽

Chloride Solution ◽

Sodium Chloride Solution ◽

Aqueous Sodium Chloride Solution ◽

Aqueous Sodium

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Ab initio calculations on the effect of different basis sets and electron correlation on the transition state for the reactions HNC ? HCN and BCN ? BNC

Journal of Computational Chemistry ◽

10.1002/jcc.540050102 ◽

1984 ◽

Vol 5 (1) ◽

pp. 1-10 ◽

Cited By ~ 12

Author(s):

Christopher Glidewell ◽

Colin Thomson

Keyword(s):

Transition State ◽

Ab Initio Calculations ◽

Ab Initio ◽

Electron Correlation ◽

Basis Sets

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Transition state dynamics and a QM/MM model for the Cl + C2H5Cl SN2 reaction

Canadian Journal of Chemistry ◽

10.1139/v04-082 ◽

2004 ◽

Vol 82 (6) ◽

pp. 891-899 ◽

Cited By ~ 14

Author(s):

Lipeng Sun ◽

Eunkyung Chang ◽

Kihyung Song ◽

William L Hase

Keyword(s):

Hydrogen Atom ◽

Transition State ◽

Reaction Dynamics ◽

Vibrational Frequencies ◽

Dynamics Simulation ◽

Rrkm Theory ◽

Direct Dynamics ◽

Sn2 Reaction ◽

Classical Trajectories ◽

Link Atom

A MP2/6-31G* direct dynamics simulation is used to study the dynamics of the central barrier [Cl-C2H5-Cl] for the Cl + C2H5 SN2 reaction. The majority of the trajectories move off the central barrier to form the ClC2H5Cl complex and appear to undergo efficient IVR as assumed by RRKM theory. However, some of the trajectories move directly to products without forming the complex, a non-RRKM result. A hydrogen atom link-atom QM/MM model is described for studying the dynamics of [X-CH2R-Y] central barriers with the -R substituent. The model is used to calculate vibrational frequencies for the [Cl-C2H5-Cl] central barrier.Key words: SN2 reaction dynamics, RRKM theory, QM/MM model, central barrier dynamics, direct dynamics classical trajectories.

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Ab initio calculations on the reaction mechanism for the radical reaction CH3+ClO

Physical Chemistry Chemical Physics ◽

10.1039/b100064k ◽

2001 ◽

Vol 3 (17) ◽

pp. 3662-3666 ◽

Cited By ~ 6

Author(s):

Xiaoguo Zhou ◽

Jiang Li ◽

Xin Zhao ◽

Yuan Tian ◽

Liming Zhang ◽

...

Keyword(s):

Reaction Mechanism ◽

Ab Initio Calculations ◽

Ab Initio ◽

Radical Reaction

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Conformational study on the structures and energies of the weakly bound complexes of AlCl3 with diatomic molecules

Open Chemistry ◽

10.2478/s11532-007-0046-4 ◽

2007 ◽

Vol 5 (4) ◽

pp. 1007-1018 ◽

Cited By ~ 2

Author(s):

Issac Jimenez-Fabian ◽

Abraham Jalbout ◽

Abderahim Boutalib

Keyword(s):

Transition State ◽

Ab Initio Calculations ◽

Ab Initio ◽

Conformational Study ◽

Weakly Bound ◽

Hydrogen Halides ◽

Strength Of Interaction ◽

Weakly Bound Complexes ◽

Aluminium Trichloride ◽

High Level

AbstractIn this work we present the results of high level ab initio calculations on weakly bound complexes of aluminium trichloride and hydrogen halides, HX, halogens, X2 and diatomic interhalogens, XY (where X, Y = F, Cl, Br). Based upon these calculations we have predicted that all structures in the staggered conformation (except for Cl3AlFH and Cl3AlClH) are stable minima while those in the eclipsed configurations are transition state structures. In the XH complexes the strength of interaction with the Cl3Al group is FH > ClH > BrH. In the case of X2 species it is Br2 > F2 > Cl2, and finally in the XY (YX) group it is: FBr > ClBr > FCl > BrCl > BrF > ClF.

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A study of hydrogen abstraction reactions by halogen atoms with HFCO and HClCO: determination of transition state structures, barrier heights, and vibrational frequencies

Canadian Journal of Chemistry ◽

10.1139/v93-019 ◽

1993 ◽

Vol 71 (1) ◽

pp. 135-140 ◽

Cited By ~ 6

Author(s):

J. S. Francisco ◽

N. Mina-Camilde

Keyword(s):

Transition State ◽

Ab Initio Calculations ◽

Ab Initio ◽

Chlorine Atom ◽

Fluorine Atom ◽

Hydrogen Abstraction ◽

Barrier Heights ◽

Optimized Geometries ◽

Good Agreement

Theoretical barriers and reaction energetics were determined using ab initio calculations at the PMP4/6-311 + +G** level with UMP2/6-311G** optimized geometries for hydrogen abstraction reactions of HFCO and HClCO by fluorine and chlorine atoms. The largest barriers are predicted for fluorine and chlorine atom abstractions of hydrogen from HFCO. Fluorine and chlorine atom abstractions of hydrogen from HClCO are predicted to be barrierless. The predicted barrier for fluorine atom abstraction of hydrogen from HFCO is calculated to be 1.3 kcal mol−1 and is in good agreement with the experimental value of 1.8 ± 0.4 kcal mol−1.

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