Ab initio studies of the gas-phase thermodynamic properties and bond dissociation energies for haloethanes and halomethyl radicals
文献信息
Adriana C. Olleta, Silvia I. Lane
Ab initio molecular orbital calculations have been performed on fluorine- and chlorine-substituted ethanes and radicals. The molecular equilibrium characteristics (energies, structural parameters and vibrational frequencies) of all the species were estimated at the MP2/6-311G** level of theory. A rigid harmonic oscillator model was used for the development of a data base for the ideal gas thermodynamic properties: Cp°, S°, − (G° − H0°)/T, ΔfH°, ΔfG° and log Kf, of the haloethanes and halomethyl radicals over a temperature range 0–1500 K. From the estimated enthalpies of formation at 298.15 K and 1 atm, bond dissociation energies for the homolytic cleavage of C–C bonds for the haloethanes were obtained. The results of the MP2/6-311G** calculations of the heats of formation at 298.15 K, ΔfH298.15K°, of the halogenated methyl radicals have been compared with those obtained using the CBS-RAD procedure and a modification of this called CBS-RAD(B3-LYP,B3-LYP). Finally, the influence of halogen substituents on reactivity has been interpreted in terms of polar and hyperconjugation effects.
期刊推荐

Main Group Chemistry

Bioorganic & Medicinal Chemistry

Acta Metallurgica Sinica-English Letters

Herald of the Russian Academy of Sciences

Journal of Chemical Sciences

Critical Reviews in Solid State and Materials Sciences

Medicinal Chemistry Research

Journal of the Indian Institute of Science

Heteroatom Chemistry

Polycyclic Aromatic Compounds
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.




