An investigation of the reaction of O with CH2F2 with ab initio molecular orbital calculations

LEE, E.P. F.; Dyke, J. M.

doi:10.1080/00268979609482406

Cited by 4 publications

(8 citation statements)

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“…Hydrated proton clusters have been investigated using ab initio methods, [25][26][27][28][29][30][31][32][33][34] including ab initio molecular dynamics [35][36][37] and ab initio path integral techniques. 38 Studies by Wei and Salahub 36 gave an early indication that larger proton hydrates would be less compact than their neutral counterparts, a finding consistent with our studies.…”

Section: Introductionmentioning

confidence: 99%

Topology versus temperature: Thermal behavior of H+(H2O)8 and H+(H2O)16

Singer

McDonald

Ojamäe

2000

The Journal of Chemical Physics

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Monte Carlo simulations based on the OSS2 potential indicate the structure of the small protonated water clusters, H+(H2O)8 and H+(H2O)16, is far from what could be expected for the proton solvated in bulk water. Near room temperature we find H+(H2O)n, n=8,16 clusters have a treelike topology with chains of waters emanating from a central H3O+ moiety. Only at lower temperatures do cycles and cages of water appear. These findings bear upon experiments in a variety of disciplines.

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Section: Introductionmentioning

confidence: 99%

Topology versus temperature: Thermal behavior of H+(H2O)8 and H+(H2O)16

Singer

McDonald

Ojamäe

2000

The Journal of Chemical Physics

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“…Both TS1 and IM2 have C s symmetry and the electronic states for TS1 and IM2 are both 2 A . NPA on IM2 shows [32,33], the PES of OH· · · CH 2 CN − could be viewed as low-lying electronic excited state PES of OH − · · · CH 2 CN, and nona-diabatic transition between these two lower PESs responds to the H + transfer and H-atom transfer channels. Due to the degeneracy in energy of these two PESs, IM2 has characters of both OH − · · · CH 2 CN and OH· · · CH 2 CN − .…”

Section: A H + Transfer and H-atom Transfer Reaction Channelsmentioning

confidence: 99%

Mechanistic Investigation on the Reaction of O− with CH3CN Using Density Functional Theory

Zhou

et al. 2010

Chinese Journal of Chemical Physics

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The potential energy profile of the reaction between the atomic oxygen radical anion and acetonitrile has been mapped at the G3MP2B3 level of theory. Geometries of the reactants, products, intermediate complexes, and transition states involved in this reaction have been optimized at the (U)B3LYP/6-31+G(d,p) level, and then their accurate relative energies have been improved using the G3MP2B3 method. The potential energy profile is confirmed via intrinsic reaction coordinate calculations of transition states. Four possible production channels are examined respectively, as H + transfer, H-atom transfer, H 2 + transfer, and bimolecular nucleophilic substitution (S N 2) reaction pathways. Based on present calculations, the H 2 + transfer reaction is major among these four channels, which agrees with previous experimental conclusions.

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“…The general strategy used and the details of the calculations performed follow our recent work on the study of the reaction O - + CH 2 F 2 → products, and therefore will only be summarized here. In brief, the reaction paths of the two main reaction channels observed experimentally (see next section) were studied at the HF/6-31++G ** and MP2/6-31++G ** levels by carrying out geometry optimization (to locate intermediates), transition-state (TS) search, and intrinsic reaction coordinate (IRC) calculations.…”

Section: Computational Detailsmentioning

confidence: 99%

“…In this connection, kinetic studies of relevant gas-phase reactions involving HFCs and the understanding of their reaction mechanisms would assist in understanding their fates in the atmosphere. We have recently published a detailed ab initio and selected ion flow tube (SIFT) study of the reaction O - + CH 2 F 2 → products . This present study of the reaction OH - + CH 2 F 2 → products is an extension of this work and is part of a larger program of work to investigate anion−molecule reactions of importance in the upper atmosphere.…”

Section: Introductionmentioning

confidence: 97%

“…In the case of the reaction O - + CH 2 F 2 → products, the reaction mechanisms are rather complex . However, based on the results of the ab initio calculations, it was concluded that all the observed reaction channels proceed via a reactant-like anion−molecular complex, O - ·CH 2 F 2 , followed by crossing onto the OH·CHF 2 - surface.…”

Section: Introductionmentioning

confidence: 99%

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Study of the OH^- + CH₂F₂ Reaction by Selected Ion Flow Tube Experiments and ab Initio Calculations

1998

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The reaction OH -+ CH 2 F 2 f products has been investigated by both selected ion flow tube (SIFT) experiments and ab initio molecular calculations. The SIFT experiments showed that a bimolecular process, leading to two major anionic products, CHF 2 -(86%) and F -(11%), and one minor anionic product, HF 2 -(3%), is in competition with a three-body association leading to OH -‚CH 2 F 2 (where values in parentheses are the relative values of the detected anionic products at 300 K). From a pressure dependence study, an upper limit of the bimolecular reaction rate coefficient at 300 K is determined to be (2.4 ( 1.4) × 10 -12 cm 3 molecule -1 s -1 . This shows a small negative temperature dependence, suggesting that the reaction proceeds via an ion-complex intermediate. These experimental results were rationalized using ab initio molecular orbital calculations. Stationary points on the reaction paths of the two main reaction channels were located at both the HF/6-31++G ** and MP2/6-31++G ** levels. The relative energies of the located stationary points were calculated at up to the CCSD(T)/6-311++G 3df,2p //MP2/6-31++G ** level. The CHF 2 -+ H 2 O channel was found to be endothermic by 7.5 kcal mol -1 and the F -+ CH 2 (OH)F channel was found to be exothermic by 20.4 kcal mol -1 . It was found that both reaction channels proceed via the reactant-like ion-molecule complex intermediate, OH -‚CH 2 F 2 , in agreement with the conclusion drawn from the experimental negative temperature dependence of the overall rate coefficient. The fact that the product anion yields show that [CHF 2 -] > [F -], despite the fact that the CHF 2 -+ H 2 O channel is endothermic whereas the F -+ CH 2 (OH)F channel is exothermic, has been rationalized using transition-state theory.

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An investigation of the reaction of O with CH2F2 with ab initio molecular orbital calculations

Cited by 4 publications

References 0 publications

Topology versus temperature: Thermal behavior of H+(H2O)8 and H+(H2O)16

Topology versus temperature: Thermal behavior of H+(H2O)8 and H+(H2O)16

Mechanistic Investigation on the Reaction of O− with CH3CN Using Density Functional Theory

Study of the OH^- + CH₂F₂ Reaction by Selected Ion Flow Tube Experiments and ab Initio Calculations

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An investigation of the reaction of O with CH2F2 with ab initio molecular orbital calculations

Cited by 4 publications

References 0 publications

Topology versus temperature: Thermal behavior of H+(H2O)8 and H+(H2O)16

Topology versus temperature: Thermal behavior of H+(H2O)8 and H+(H2O)16

Mechanistic Investigation on the Reaction of O− with CH3CN Using Density Functional Theory

Study of the OH- + CH2F2 Reaction by Selected Ion Flow Tube Experiments and ab Initio Calculations

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Study of the OH^- + CH₂F₂ Reaction by Selected Ion Flow Tube Experiments and ab Initio Calculations