Analysis of the rates of ion-molecule association reactions. Proton-bound dimers of ammonia, methylamine, and dimethylamine

Olmstead, William N.; Lev‐on, Miriam; Golden, David M.; Brauman, John I.

doi:10.1021/ja00446a003

Cited by 61 publications

(25 citation statements)

References 10 publications

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“…The relations eq [14][15][16][17][18][19] apply as well to reactions where higher barriers appear in the forward and backward directions. However, E0(J) -E0(J=0) then has to be determined in a different way in order to obtain the parameters C" and v of eq 17.…”

Section: Dissociation and Recombination Rate Constants At Low Pressuresmentioning

confidence: 99%

Predictive possibilities of unimolecular rate theory

Troe¹

1979

J. Phys. Chem.

835

778

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This paper describes the calculation of rate constants for thermal unimolecular reactions and recombinations at the low pressure limit, at the high pressure limit, and in the intermediate falloff range, as well as the calculation of specific rate constants for unimolecular rearrangements. The most uncertain factors of the theory are identified by comparison with the N02, CIÑO, H20, and 03 systems. Weak collision and centrifugal barrier effects are discussed for low pressure rate constants. Simplified adiabatic channel calculations are proposed for specific rate constants and high pressure rate constants. Reduced falloff curves are presented in factorized form with weak collision and strong collision broadening factors. Simple falloff expressions are derived.

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Section: Dissociation and Recombination Rate Constants At Low Pressuresmentioning

confidence: 99%

Predictive possibilities of unimolecular rate theory

Troe¹

1979

J. Phys. Chem.

835

778

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“…Further investigations involving 13CF,H' and GF2Df are planned to deduce which of these schemes is operative in this system. We are currently extending our studies of birnolecular production of cluster ions to the gas phase ion chemistry of other weak bases with tetrafluorodimethyl ether and other polyfluorinated ethers, with the ultimate aim of developing a scale of relative solvation energetics based on examination of equilibria such as reaction [ 2 ] .…”

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confidence: 99%

Bimolecular production of gas phase ionic hydrates by ion cyclotron resonance spectroscopy

Clair¹,

McMahon²

1980

Can. J. Chem.

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The gas phase ion–molecule reactions of α,α,α′,α′ tetrafluorodimethyl ether both alone and in mixtures with water have been examined. The dominant feature of the ion chemistry of these mixtures is the sequential bimolecular production of the hydrated hydronium ion, H5O2+. Two independent mechanistic pathways for production of H5O2+ are outlined arising from reaction of H3O+ with (CF2H)2O and from CF2H—O=CHF+ with H2O. Implications for examination of solvent switching equilibria are discussed.

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“…Thus, their energy distributions are not Boltzmann, and the reactions cannot be treated in terms of the Arrhenius equation. We have discussed this problem previously (9,10), and appropriate recipes are well documented (11,12).…”

Section: Analysis Of Gas-phase Dynamicsmentioning

confidence: 99%

Intrinsic Nucleophilicity

Brauman

Dodd

Han

1987

Advances in Chemistry

Self Cite

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Nucleophilic displacement reactions of anions with neutral alkyl halides were studied in the gas phase by using mass spectrometric techniques. Analysis of the rates of the reactions leads to a model of the potential surface, which has a double minimum. The energetics associated with the surface can be obtained and with the use of Marcus theory leads to an estimate of the energy of the self-exchange reaction, Y-+ CH 3 Y -> CH 3 Y + Y-. The energies for self-exchange are suggested as a measure of the intrinsic nucleophilicity of Y-. The relationship of proton affinity and methyl cation affinity (carbon basicity) is analyzed.1SIUCLEOPHILIC DISPLACEMENT REACTIONS occupy a unique place in organic chemistry. These reactions are among the most studied and have played a critical role in numerous models of reaction chemistry such as steric effects, polar effects, solvent effects, and structure-reactivity correlations. Nucleophilic displacement reactions have been prominent in the develop ment of paradigms for studying stereochemistry as well. In some sense, the nucleophilic displacement reaction is also among the best understood of chemical reactions, and this reaction occupies a critical place in the pedagogy of elementary organic chemistry. Nevertheless, the area still has major conceptual problems associated with it, as evidenced by the papers pre sented in the symposium upon which this book is based.In fact, why some reactions are fast and others slow is often difficult to explain in simple terms, and prediction of the rates of reactions is essentially impossible without either an elaborate quantum calculation or the use of a complex set of empirical parameters. Our work in studying simple S N 2 reactions in the gas phase has been aimed at developing a view of these reactions that can be understood in relatively elementary terms. By remov ing the effects of solvation, we hope to discern the important factors involved in determining reaction rates. Although our efforts are far from complete, we believe that the reactions can now be understood, at least in the first approximation (1-8).

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Analysis of the rates of ion-molecule association reactions. Proton-bound dimers of ammonia, methylamine, and dimethylamine

Cited by 61 publications

References 10 publications

Predictive possibilities of unimolecular rate theory

Predictive possibilities of unimolecular rate theory

Bimolecular production of gas phase ionic hydrates by ion cyclotron resonance spectroscopy

Intrinsic Nucleophilicity

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