Magnesium porphyrin radical cations: a theoretical study of substituent effects on the ground state

1992 ◽  
Vol 114 (24) ◽  
pp. 9538-9544 ◽  
Author(s):  
A. Geoffrey Skillman ◽  
Jack R. Collins ◽  
Gilda H. Loew
Keyword(s):  
Ground State ◽  
Theoretical Study ◽  
Substituent Effects ◽  
Radical Cations

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+.

POLARON IN A QUANTUM DOT UNDER AN ELECTRIC FIELD

2007 ◽  
Vol 21 (24) ◽  
pp. 1635-1642
Author(s):  
MIAN LIU ◽  
WENDONG MA ◽  
ZIJUN LI
Keyword(s):  
Quantum Dot ◽  
Electric Field ◽  
Field Intensity ◽  
Ground State Energy ◽  
Ground State ◽  
Electric Field Intensity ◽  
State Energy ◽  
Theoretical Study ◽  
The Moment ◽  
Transformation Methods

We conducted a theoretical study on the properties of a polaron with electron-LO phonon strong-coupling in a cylindrical quantum dot under an electric field using linear combination operator and unitary transformation methods. The changing relations between the ground state energy of the polaron in the quantum dot and the electric field intensity, restricted intensity, and cylindrical height were derived. The numerical results show that the polar of the quantum dot is enlarged with increasing restricted intensity and decreasing cylindrical height, and with cylindrical height at 0 ~ 5 nm , the polar of the quantum dot is strongest. The ground state energy decreases with increasing electric field intensity, and at the moment of just adding electric field, quantum polarization is strongest.

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.

Theoretical Study of the Fragmentation Pathways of Norbornane in Its Doubly Ionized Ground State

2007 ◽  
Vol 111 (42) ◽  
pp. 10834-10848 ◽  
Author(s):  
Stefan Knippenberg ◽  
Balázs Hajgató ◽  
Jean-Pierre François ◽  
Michael S. Deleuze
Keyword(s):  
Ground State ◽  
Theoretical Study ◽  
Fragmentation Pathways
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