Kinetics and mechanism of diallyl sulfoxide pyrolysis; a combined theoretical and experimental study in the gas phase

RSC Advances ◽  
2014 ◽  
Vol 4 (108) ◽  
pp. 62809-62816 ◽  
Author(s):  
M. Izadyar ◽  
M. R. Gholami
Keyword(s):  
Experimental Study ◽  
Gas Phase ◽  
Computational Study ◽  
Kinetics And Mechanism ◽  
Pyrolysis Reaction

A combined experimental and computational study was carried out on the gas phase pyrolysis reaction of diallylsulfoxide.

Experimental Study of Gas-Phase Pyrolysis Reaction of Benzene to Investigate the Early Stage of Coke Formation

2014 ◽  
Vol 47 (5) ◽  
pp. 406-415 ◽  
Author(s):  
Akihiro Kousoku ◽  
Ryuichi Ashida ◽  
Akio Miyasato ◽  
Mikio Miyake ◽  
Kouichi Miura
Keyword(s):  
Experimental Study ◽  
Gas Phase ◽  
Early Stage ◽  
Coke Formation ◽  
Pyrolysis Reaction

Explaining the magnetism of gold

2017 ◽  
Author(s):  
Robson de Farias
Keyword(s):  
Gas Phase ◽  
Computational Study ◽  
Formation Enthalpy ◽  
Gold Atom ◽  
Orbital Energy ◽  
Knudsen Effusion ◽  
Energy Diagram ◽  
Unpaired Electrons ◽  
The Difference ◽  
Good Agreement

<p>In the present work, a computational study is performed in order to clarify the possible magnetic nature of gold. For such purpose, gas phase Au<sub>2</sub> (zero charge) is modelled, in order to calculate its gas phase formation enthalpy. The calculated values were compared with the experimental value obtained by means of Knudsen effusion mass spectrometric studies [5]. Based on the obtained formation enthalpy values for Au<sub>2</sub>, the compound with two unpaired electrons is the most probable one. The calculated ionization energy of modelled Au<sub>2</sub> with two unpaired electrons is 8.94 eV and with zero unpaired electrons, 11.42 eV. The difference (11.42-8.94 = 2.48 eV = 239.29 kJmol<sup>-1</sup>), is in very good agreement with the experimental value of 226.2 ± 0.5 kJmol<sup>-1</sup> to the Au-Au bond<sup>7</sup>. So, as expected, in the specie with none unpaired electrons, the two 6s<sup>1</sup> (one of each gold atom) are paired, forming a chemical bond with bond order 1. On the other hand, in Au<sub>2</sub> with two unpaired electrons, the s-d hybridization prevails, because the relativistic contributions. A molecular orbital energy diagram for gas phase Au<sub>2</sub> is proposed, explaining its paramagnetism (and, by extension, the paramagnetism of gold clusters and nanoparticles).</p>

2-Deoxyribose Radicals in the Gas Phase and Aqueous Solution. Transient Intermediates of Hydrogen Atom Abstraction from 2-Deoxyribofuranose

2005 ◽  
Vol 70 (11) ◽  
pp. 1769-1786 ◽  
Author(s):  
Luc A. Vannier ◽  
Chunxiang Yao ◽  
František Tureček
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Atom ◽  
Gas Phase ◽  
Computational Study ◽  
Hydrogen Atom Abstraction ◽  
Oh Radical ◽  
Free Energies ◽  
Intramolecular Hydrogen ◽  
Solvation Free Energies ◽  
Transient Intermediates

A computational study at correlated levels of theory is reported to address the structures and energetics of transient radicals produced by hydrogen atom abstraction from C-1, C-2, C-3, C-4, C-5, O-1, O-3, and O-5 positions in 2-deoxyribofuranose in the gas phase and in aqueous solution. In general, the carbon-centered radicals are found to be thermodynamically and kinetically more stable than the oxygen-centered ones. The most stable gas-phase radical, 2-deoxyribofuranos-5-yl (5), is produced by H-atom abstraction from C-5 and stabilized by an intramolecular hydrogen bond between the O-5 hydroxy group and O-1. The order of radical stabilities is altered in aqueous solution due to different solvation free energies. These prefer conformers that lack intramolecular hydrogen bonds and expose O-H bonds to the solvent. Carbon-centered deoxyribose radicals can undergo competitive dissociations by loss of H atoms, OH radical, or by ring cleavages that all require threshold dissociation or transition state energies >100 kJ mol-1. This points to largely non-specific dissociations of 2-deoxyribose radicals when produced by exothermic hydrogen atom abstraction from the saccharide molecule. Oxygen-centered 2-deoxyribose radicals show only marginal thermodynamic and kinetic stability and are expected to readily fragment upon formation.

A vibrational spectroscopic and computational study of the structures of protonated imidacloprid and its fragmentation products in the gas phase

2021 ◽  
Vol 23 (5) ◽  
pp. 3377-3388
Author(s):  
Kelsey J. Menard ◽  
Jonathan Martens ◽  
Travis D. Fridgen
Keyword(s):  
Computational Chemistry ◽  
Gas Phase ◽  
Vibrational Spectroscopy ◽  
Computational Study ◽  
Unimolecular Decomposition ◽  
Decomposition Products

Vibrational spectroscopy and computational chemistry studies were combined with the aim of elucidating the structures of protonated imidacloprid (pIMI), and its unimolecular decomposition products.

scholarly journals A New Computational Method for Estimating Simultaneous Equations Models Using Entropy as a Parameter Criteria

Mathematics ◽  
2021 ◽  
Vol 9 (7) ◽  
pp. 700
Author(s):  
Belén Pérez-Sánchez ◽  
Martín González ◽  
Carmen Perea ◽  
Jose J. López-Espín
Keyword(s):  
Experimental Study ◽  
Computational Study ◽  
Estimation Method ◽  
Information Criteria ◽  
Simultaneous Equations ◽  
Estimation Methods ◽  
Entropy Measure ◽  
Economic Science ◽  
Akaike Information Criteria ◽  
Simultaneous Equations Models

Simultaneous Equations Models (SEM) is a statistical technique widely used in economic science to model the simultaneity relationship between variables. In the past years, this technique has also been used in other fields such as psychology or medicine. Thus, the development of new estimating methods is an important line of research. In fact, if we want to apply the SEM to medical problems with the main goal being to obtain the best approximation between the parameters of model and their estimations. This paper shows a computational study between different methods for estimating simultaneous equations models as well as a new method which allows the estimation of those parameters based on the optimization of the Bayesian Method of Moments and minimizing the Akaike Information Criteria. In addition, an entropy measure has been calculated as a parameter criteria to compare the estimation methods studied. The comparison between those methods is performed through an experimental study using randomly generated models. The experimental study compares the estimations obtained by the different methods as well as the efficiency when comparing solutions by Akaike Information Criteria and Entropy Measure. The study shows that the proposed estimation method offered better approximations and the entropy measured results more efficiently than the rest.

Sign in / Sign up

Export Citation Format

Share Document