scholarly journals Experimental and Theoretical Study of the Enthalpy of Formation of 3,6-Diphenyl-1,2,4,5-Tetroxane Molecule

2002 ◽  
Vol 2 ◽  
pp. 455-460 ◽  
Author(s):  
N.L. Jorge ◽  
L.C.A. Leiva ◽  
M.G. Castellanos ◽  
M.E. Gomez Vara ◽  
L.F.R. Cafferata ◽  
...  
Keyword(s):  
Vapor Pressure ◽  
Enthalpy Of Formation ◽  
Vapor Phase ◽  
Theoretical Study ◽  
Theoretical Calculations ◽  
Basis Set ◽  
Sublimation Enthalpy ◽  
Combustion Heat ◽  
Different Temperatures ◽  
The Enthalpy Of Formation

We report the results obtained for the experimental determination and the theoretical calculation of the enthalpy of formation of 3,6-diphenyl-1,2,4,5-tetroxane molecule. The experimental work was performed using a macrocalorimeter to measure the combustion heat, and the sublimation enthalpy was determined via the measurement of the vapor pressure at equilibrium with the vapor phase at different temperatures resorting to the Clapeyron-Claussius equation. Theoretical calculations were performed using semiempirical AM1 and PM3 methods as well asab initiotechniques at the 3-21, 6-31G(d,p), and 6-311G(d,p) basis set levels.

scholarly journals Point Defects in Materials Part I: Behavior and Characteristics in Different Material Classes

MRS Bulletin ◽  
1991 ◽  
Vol 16 (11) ◽  
pp. 28-32
Author(s):  
David N. Seidman ◽  
Donglu Shi
Keyword(s):  
Enthalpy Of Formation ◽  
Point Defects ◽  
Theoretical Calculations ◽  
Pure Copper ◽  
Historical Review ◽  
Enthalpies Of Formation ◽  
Professor Emeritus ◽  
Face Centered Cubic ◽  
Interstitial Atoms ◽  
The Enthalpy Of Formation

In this issue of the MRS Bulletin we present five papers that involve point defect phenomena in a wide variety of materials—metals, conducting ceramic oxides, semiconductors, amorphous alloys, and high Tc superconducting oxides. The unifying theme of this issue is point defects—zero-dimensional defects. Even for the high Tc oxides, where planar defects are discussed, it is the ordering of oxygen/vacancy chains that ultimately gives rise to twins in the famous YBa2Cu3O7.δ (1:2:3) oxide superconductor.Hillard Huntington, professor emeritus of physics at Rensselaer Polytechnic Institute, is an early and important pioneer in the study of point defects in metals. A theorist, he has also performed many experiments over the years; for example, he performed key early experiments on electromigration effects. Huntington's article presents a historical review of the research on vacancies and self-interstitial atoms in metals during the period that stretches from the mid-1930s to the mid-1960s. He played a crucial role in this field as a result of his seminal theoretical calculations, with Fred Seitz in 1942, on the enthalpies of formation and migration of vacancies or self-interstitial atoms in pure copper. Huntington's and Seitz's calculations indicated that diffusion occurs predominantly by a monovacancy mechanism since the enthalpy of formation of a self-interstitial atom, the [100] split form, also called the dumbbell form, is too large to be compatible with the activation enthalpy for self-diffusion in copper. It is now well established that the latter is given by the sum of the enthalpy of formation and the enthalpy of migration of a monovacancy in many face-centered-cubic (fcc), body-centered-cubic (bec), and hexagonal-close-packed (hcp) metals.

The enthalpy of formation of the pentane-2,4-dionate radical: A complete basis set approach

2006 ◽  
Vol 419 (4-6) ◽  
pp. 486-491 ◽  
Author(s):  
P. Cabral do Couto ◽  
Benedito J. Costa Cabral ◽  
José A. Martinho Simões
Keyword(s):  
Enthalpy Of Formation ◽  
Basis Set ◽  
Complete Basis ◽  
Complete Basis Set ◽  
The Enthalpy Of Formation

Comparison of an intramolecular Michael-type addition with its intermolecular counterpart: an abinitio theoretical study

1989 ◽  
Vol 67 (12) ◽  
pp. 2173-2177 ◽  
Author(s):  
C. I. Bayly ◽  
F. Grein
Keyword(s):  
Transition State ◽  
Michael Addition ◽  
State Energy ◽  
Theoretical Study ◽  
Theoretical Calculations ◽  
Single Point ◽  
Basis Set ◽  
Energy Change ◽  
Transition State Geometry ◽  
Michael Type Addition

Abinitio theoretical calculations were carried out on the intramolecular addition of 3-ketopent-4-en-1-olate 1 to form 1-oxacyclohex-3-en-4-olate 2 (reaction I; Scheme 1) and the corresponding intermolecular Michael addition of methanolate to butenone forming 4-methoxybut-2-en-2-olate 4 (reaction II; Scheme 1). The calculations were carried out at the RHF level using an augmented 4-31G basis set; single point energies were then taken using the 6-31 + G* basis set. The overall energy change of the reaction in going from reactants to products is very similar for both reactions, with products being about 8.3 kcal/mol more stable than reactants; the major difference energetically between the two reactions is at the level of the transition state: the transition state energy for reaction I (intramolecular) is 6 kcal/mol higher than that for reaction II (intermolecular). The transition state geometry of reaction II conforms quite closely to the stereoelectronic requirements for a Michael addition, but that of reaction I is very distorted, reflecting significant compromises in the stereoelectronic requirements. Keywords: abinitio theoretical study, Michael-type addition, intramolecular, transition state.

A theoretical study towards thermolysis process of thionesters and thiolesters

2018 ◽  
Vol 17 (02) ◽  
pp. 1850014 ◽  
Author(s):  
Xun Zhu ◽  
Xiuqin Zhou ◽  
Dongsheng Xiang ◽  
Ping Wu
Keyword(s):  
Theoretical Study ◽  
Theoretical Calculations ◽  
Transition States ◽  
Membered Ring ◽  
Basis Set ◽  
Reaction Progress ◽  
Alkyl Groups ◽  
Thermal Elimination ◽  
Bond Indices ◽  
Wiberg Bond Indices

This paper focuses on the thermal elimination of alkenes from methyl alkyl thionacetates and thiolacetates. Three alkyl groups are calculated: ethyl, isopropyl and tert-butyl. Possible elimination mechanisms are considered, including six- and four-membered ring transition states for alkene elimination, four-membered ring isomerization and a possible five-membered ring decomposition. Theoretical calculations are performed with the MP2 method and the 6-31G* basis set. Wiberg bond indices are also summarized to monitor the reaction progress.

scholarly journals The SN2 reaction and its relationship with the Walden inversion, the Finkelstein and Menshutkin reactions together with theoretical calculations for the Finkelstein reaction

2021 ◽  
Author(s):  
Ibon Alkorta ◽  
José Elguero
Keyword(s):  
Linear Models ◽  
Theoretical Calculations ◽  
Computational Method ◽  
Basis Set ◽  
Free Energies ◽  
Nitrogen And Phosphorus ◽  
Atom Pairs ◽  
Leaving Groups ◽  
First Time ◽  
Nitrogen Phosphorus

AbstractThis communication gives an overview of the relationships between four reactions that although related were not always perceived as such: SN2, Walden, Finkelstein, and Menshutkin. Binary interactions (SN2 & Walden, SN2 & Menshutkin, SN2 & Finkelstein, Walden & Menshutkin, Walden & Finkelstein, Menshutkin & Finkelstein) were reported. Carbon, silicon, nitrogen, and phosphorus as central atoms and fluorides, chlorides, bromides, and iodides as lateral atoms were considered. Theoretical calculations provide Gibbs free energies that were analyzed with linear models to obtain the halide contributions. The M06-2x DFT computational method and the 6-311++G(d,p) basis set have been used for all atoms except for iodine where the effective core potential def2-TZVP basis set was used. Concerning the central atom pairs, carbon/silicon vs. nitrogen/phosphorus, we reported here for the first time that the effect of valence expansion was known for Si but not for P. Concerning the lateral halogen atoms, some empirical models including the interaction between F and I as entering and leaving groups explain the Gibbs free energies.

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