A computational study into the reactivity of epichlorohydrin and epibromohydrin under acidic conditions in the gas phase and aqueous solution

2007 ◽  
Vol 20 (12) ◽  
pp. 1058-1071 ◽  
Author(s):  
E. S. Shields ◽  
G. N. Merrill
Keyword(s):  
Aqueous Solution ◽  
Gas Phase ◽  
Computational Study ◽  
Acidic Conditions

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.

Computational study on hydrolysis of cefotaxime in gas phase and in aqueous solution

2012 ◽  
Vol 33 (24) ◽  
pp. 1948-1959 ◽  
Author(s):  
Conchín Meliá ◽  
Silvia Ferrer ◽  
Vicent Moliner ◽  
Iñaki Tuñón ◽  
Juan Bertrán
Keyword(s):  
Aqueous Solution ◽  
Gas Phase ◽  
Computational Study ◽  
Hydrolysis Of

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>

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.

Simulation of UV Absorption Spectra and Relaxation Dynamics of Uracil and Uracil-Water Clusters

2020 ◽  
Author(s):  
Branislav Milovanović ◽  
Jurica Novak ◽  
Mihajlo Etinski ◽  
Wolfgang Domcke ◽  
Nadja Doslic
Keyword(s):  
Aqueous Solution ◽  
Gas Phase ◽  
Absorption Spectra ◽  
Absorption Spectroscopy ◽  
Water Clusters ◽  
Uv Absorption ◽  
Relaxation Dynamics ◽  
Nonradiative Relaxation ◽  
Uv Absorption Spectra ◽  
Uv Absorption Spectroscopy

Despite many studies, the mechanisms of nonradiative relaxation of uracil in the gas phase and in aqueous solution are still not fully resolved. Here we combine theoretical UV absorption spectroscopy...

scholarly journals Thermo-Responsive Behavior of Mixed Aqueous Solution of Hydrophilic Polymer with Pendant Phosphorylcholine Group and Poly(Acrylic Acid)

Polymers ◽  
2021 ◽  
Vol 13 (1) ◽  
pp. 148
Author(s):  
Hirokazu Fukumoto ◽  
Kazuhiko Ishihara ◽  
Shin-Ichi Yusa
Keyword(s):  
Aqueous Solution ◽  
Acrylic Acid ◽  
Solution Temperature ◽  
Interpolymer Complex ◽  
Mixed Aqueous Solution ◽  
Upper Critical Solution Temperature ◽  
Acidic Conditions ◽  
Decreasing Ph ◽  
Increasing Temperature ◽  
Poly Acrylic Acid

A mixed aqueous solution of hydrophilic poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) and poly(acrylic acid) (PAAc) becomes cloudy under acidic conditions at room temperature. The pendant carboxylic acid groups in PAAc form hydrogen bonds with the ester and phosphate groups in PMPC. While the polymers aggregate under acidic conditions, neither one associate under basic conditions because of the deprotonation of the pendant carboxy groups in PAAc. We observed that the interpolymer complex formed from PMPC, and PAAc was dissociated in aqueous solutions with increasing temperature, which is an upper critical solution temperature behavior. With increasing temperature, the molecular motion increased to dissociate the interpolymer complex. The phase transition temperature increased with increasing polymer and salt concentrations, and with decreasing pH.

Sign in / Sign up

Export Citation Format

Share Document