DIRECT DENSITY FUNCTIONAL THEORY DYNAMICS STUDY FOR THE CH3OCF2CF2OCH3 + OH REACTION

2011 ◽  
Vol 10 (02) ◽  
pp. 231-244 ◽  
Author(s):  
HONG-BO YU ◽  
FENG-CHAO CUI ◽  
YONG-XIA WANG ◽  
HONG-XIA LIU ◽  
JING-YAO LIU
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Theoretical Data ◽  
State Theory ◽  
Stationary Points ◽  
Enthalpies Of Formation ◽  
Oh Radicals ◽  
Isodesmic Reactions ◽  
Functional Theory ◽  
Barrier Heights

The mechanism and kinetics of the reaction of CH3OCF2CF2OCH3 with OH radicals have been studied theoretically by a direct density functional theory dynamics method. All possible H -abstraction channels and displacement processes taking place on two different conformers of CH3OCF2CF2OCH3 have been taken into consideration. The potential energy surface information including the optimized geometries and harmonic vibrational frequencies of all the stationary points and barrier heights involved in these channels were obtained at the BB1K/6-31+G(d,p) level of theory. The rate constants were calculated using improved canonical variational transition state theory (ICVT) with the small-curvature tunneling correction (SCT) over the temperature range of 200–2000 K. The overall rate constant for the title reaction, which was obtained by considering the weight factor of each conformer from the Boltzman distribution function, is in reasonable agreement with the available experimental value. Three-term Arrhenius expression is fitted to be k T = 1.56 × 10-20 T 2.47 exp (-124.64/ T ) cm 3 molecule-1 s-1 (200–2000 K). Also, the enthalpies of formation of the reactant CH3OCF2CF2OCH3 and product radicals CH3OCF2CF2OCH2 and CH3OCF2CF2O , which lack experimental or theoretical data, were evaluated via applying isodesmic reactions.

A time-dependent density functional theory (TDDFT) interpretation of the optical spectra of zinc phthalocyanine π-cation and π-anion radicals

2009 ◽  
Vol 87 (7) ◽  
pp. 994-1005 ◽  
Author(s):  
Angela Rosa ◽  
Giampaolo Ricciardi
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Cation Radical ◽  
State Theory ◽  
Time Dependent ◽  
Zinc Phthalocyanine ◽  
Functional Theory ◽  
Satisfactory Description ◽  
Dependent Density ◽  
Anion Radicals

The UV–visible and near-IR spectra of the zinc phthalocyanine π-cation and π-anion radicals, [ZnPc(–1)]•+ and [ZnPc(–3)]•–, are investigated by time-dependent density functional theory (TDDFT) calculations using the pure, asymptotically correct, statistical average of (model) orbital potentials (SAOP) functional. The nature and intensity of the main spectral features are highlighted and interpreted on the basis of the ground-state electronic structure of the complexes. Similarities and differences with previous TDDFT/B3LYP results are discussed. TDDFT/SAOP results for the π-anion radical prove to be in excellent agreement with the solution spectra and generally in line with deconvolution analyses of solution absorption and magnetic circular dichroism (MCD) spectra. On the basis of these results a novel interpretation of the Q-band system is proposed. For the π-cation radical TDDFT/SAOP calculations provide a satisfactory description of the UV region of the spectrum. However, they do not reproduce accurately the energy and intensity of the Q band observed at 825 nm. The description of the Q-band region appears to be complicated by the presence of spurious non-Gouterman transitions. Furthermore, the calculations, either in the gas phase or in solution, do not account for the broad absorption near 500 nm that has been suggested to arise from a nondegenerate, z-polarized 2A2g excited state. Theory and experiment can be reconciled if the presence of an axial ligand such as CN– is explicitly considered in the calculations. TDDFT/SAOP results for the axially ligated [ZnPc(–1)(CN)]• species indicate that the 500 nm feature is related to the axial ligation induced symmetry lowering of the π-cation radical and this band is assigned to a z-polarized transition associated with the hole in the 2a1u.

scholarly journals Cephalexin Degradation Initiated by OH Radicals: Theoretical Prediction of the Mechanisms and the Toxicity of Byproducts

2021 ◽  
Author(s):  
R. Masmoudi ◽  
S. Khettaf ◽  
A. Soltani ◽  
A. Dibi ◽  
L. Messaadia ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Theoretical Prediction ◽  
Hydroxyl Radical ◽  
Density Functional ◽  
Aquatic Organisms ◽  
Addition Reactions ◽  
Oh Radicals ◽  
Functional Theory ◽  
Radical Attack ◽  
Mechanism Of The Reaction

Abstract In this work, density functional theory is used to study the local reactivity of cephalexin (CLX) to radical attack and explain the mechanism of the reaction between CLX and hydroxyl radical attack leading to degradation byproducts. The reaction between •OH and CLX is supposed to lead to either an addition of a hydroxyl radical or an abstraction of a hydrogen. The results showed that the affinity of cephalexin for addition reactions increases as it passes from the gas to the aqueous phase and decreases as it passes from the neutral to the ionized form. Thermodynamic data confirmed that OH addition radicals (Radd) are thermodynamically favored over H abstraction radicals (Rabs). The ecotoxicity assessments of CLX and its byproducts are estimated from the acute toxicities toward green algae, Daphnia and fish. The formation of byproducts is safe for aquatic organisms, and only one byproduct is harmful to Daphnia.

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