Electrostatic effects on ionization equilibria: An MNDO study of proton and hydrogen transfer reactions of 4-fluorobutylamine

1990 ◽  
Vol 55 (1) ◽  
pp. 1-9 ◽  
Author(s):  
Zdeněk Friedl ◽  
Stanislav Böhm
Keyword(s):  
Hydrogen Transfer ◽  
Substituent Effects ◽  
Radical Cations ◽  
Transfer Reactions ◽  
Protonated Forms ◽  
Minor Part ◽  
Bond Strengths ◽  
Ionization Equilibria ◽  
A Minor ◽  
Gas Phase Basicities

The relative enthalpies of proton transfer δ ΔH0and homolytic bond strengths δDH0(B-H+) were calculated by the MNDO method for the sp and ap conformers of 4-flurobutylamine. The data obtained, along with the experimental gas phase basicities, are compared with the values predicted by the electrostatic theory. It is shown that the substituent polar effects FD on the basicities of amines are predominantly due to interactions in their protonated forms (X-B-H+) and/or radical-cations (X-B+.), those in the neutral species (X-B) playing a minor part. A contribution, which is considerably more significant in the sp conformer than in the ap conformer, arises probably also from substituent effects on the homolytic bond strength DH0(B-H+.

Electrostatic effects on ionization equilibria: MNDO study of proton and hydrogen transfer reactions of 5-fluoropentanoic acid

1985 ◽  
Vol 63 (5) ◽  
pp. 1068-1072 ◽  
Author(s):  
Zdenek Friedl
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Carboxylic Acids ◽  
Hydrogen Transfer ◽  
Opposite Sign ◽  
Substituent Effects ◽  
Transfer Reactions ◽  
Small Contribution ◽  
Bond Strengths ◽  
Ionization Equilibria

Relative proton transfer enthalpies δΔH0 and homolytic bond strengths δΔH0 (A—H) of sp and ap conformers of 5-fluoropentanoic acid, as well as some related aliphatic and 4-X-bicyclo[2.2.2]octane-1-carboxylic halogenoacids, have been calculated by the MNDO method. The results, together with literature data concerning the gas phase acidities, were compared with the prediction of the electrostatic theory. It is shown that the substituent effects on acidities of carboxylic acids are largely due to substituent interactions in the anions and only to a smaller extent to interactions in the neutral acids. A small contribution (about one-eighth to one-fourth as large in magnitude but of opposite sign) is possibly also made by substituent effects on homolytic bond strengths DH0 (A—H).

Electrostatic effects in ionization equilibria: An MNDO study of proton and hydrogen transfer reactions of 4-fluorobutanol

1990 ◽  
Vol 55 (12) ◽  
pp. 2880-2888 ◽  
Author(s):  
Zdeněk Friedl ◽  
Stanislav Böhm
Keyword(s):  
Hydrogen Transfer ◽  
Substituent Effects ◽  
Transfer Reactions ◽  
Molecular Orbital Calculations ◽  
Small Contribution ◽  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Ionization Equilibria ◽  
Reported Data

MNDO molecular orbital calculations have been carried out for sp and ap conformers of 4-fluorobutanol and some 4-X-bicyclo[2.2.2]octanols (X = F, Cl). The results are analyzed in terms of substituent effects on proton transfer enthalpies δ ΔH0 and homolytic bond dissociation energies δDH0 (A-H) and compared with the previously reported data for 5-fluoropentanoic acid and 4-fluorobutylamine. The results are further compared with the prediction of the electrostatic theory. It is shown that the substituent polar effect FD on the acidities of halogenoalcohols is largely due to substituent interaction in the anions and only to a smaller extent to interactions in the neutral alcohol. A small contribution (about one-tenth for the ap conformer) is probably also made by the substituent effects on homolytic bond dissociation energies DH0 (A-H).

THE ROLE OF ANTHROPONYMS IN THE SEMANTIC FIELD OF ARTISTIC WORKS

2019 ◽  
Vol 2019 (29) ◽  
pp. 66-77
Author(s):  
Lidiya Derbenyova
Keyword(s):  
Literary Work ◽  
Main Theme ◽  
Semantic Field ◽  
New Meanings ◽  
Minor Part ◽  
The One ◽  
A Minor ◽  
And Storage ◽  
Horizon Of Expectations

The article explores the role of antropoetonyms in the reader’s “horizon of expectation” formation. As a kind of “text in the text”, antropoetonyms are concentrating a large amount of information on a minor part of the text, reflecting the main theme of the work. As a “text” this class of poetonyms performs a number of functions: transmission and storage of information, generation of new meanings, the function of “cultural memory”, which explains the readers’ “horizon of expectations”. In analyzing the context of the literary work we should consider the function of antropoetonyms in vertical context (the link between artistic and other texts, and the groundwork system of culture), as well as in the context of the horizontal one (times’ connection realized in the communication chain from the word to the text; the author’s intention). In this aspect, the role of antropoetonyms in the structure of the literary text is extremely significant because antropoetonyms convey an associative nature, generating a complex mechanism of allusions. It’s an open fact that they always transmit information about the preceding text and suggest a double decoding. On the one hand, the recipient decodes this information, on the other – accepts this as a sort of hidden, “secret” sense.

scholarly journals Substituent Effects on EI-MS Fragmentation Patterns of 5-Allyloxy-1-aryl-tetrazoles and 4-Allyl-1-aryl-tetrazole-5-ones; Correlation with UV-Induced Fragmentation Channels

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3282
Author(s):  
Alina Secrieru ◽  
Rabah Oumeddour ◽  
Maria L. S. Cristiano
Keyword(s):  
Theoretical Calculations ◽  
Substituent Effects ◽  
Radical Cations ◽  
Electronic Effects ◽  
Diverse Range ◽  
The Matrix ◽  
Electron Impact Mass ◽  
Fragmentation Patterns ◽  
Tetrazole Derivatives ◽  
Impact Mass

1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products.

Formation and dynamics of Saturn and its disk simulated by using a new N-body model

Open Physics ◽  
2003 ◽  
Vol 1 (4) ◽  
Author(s):  
A. Pavlov ◽  
Y. Pavlova
Keyword(s):  
Surface Density ◽  
Electromagnetic Interaction ◽  
The Core ◽  
Body Model ◽  
Magnetic Forces ◽  
Axis Of Rotation ◽  
Gravitational Model ◽  
Minor Part ◽  
Body Self ◽  
A Minor

AbstractThe formation of Saturn and its disk is simulated using a new N-body self-gravitational model. It is demonstrated that the formation of the disk and the planet is the result of gravitational contraction of a slowly rotated particle cloud that have a shape of slightly deformed sphere. The sphere was flattened by a coefficient of 0.8 along the axis of rotation. During the gravitational contraction, the major part of the cloud transformed into a planet and a minor part transformed into a disk. The thin structured disk is a result of the electromagnetic interaction in which the magnetic forces acting on charged particles of the cloud originate in the core of the planet. The simulation program gives such parameters of Saturn as the escape velocity of about 35 km/s at the surface, density, rotational velocities of the rings and temperature distribution.

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