Utilize este identificador para referenciar este registo:
https://hdl.handle.net/10316/10340
Título: | Absolute Rate Calculations for Atom Abstractions by Radicals: Energetic, Structural and Electronic Factors | Autor: | Arnaut, Luís G. Pais, Alberto A. C. C. Formosinho, Sebastião J. Barroso, Mónica |
Data: | 30-Abr-2003 | Editora: | American Chemical Society | Citação: | Journal of the American Chemical Society. 125:17 (2003) 5236-5246 | Resumo: | We calculate transition-state energies of atom-transfer reactions from reaction energies, electrophilicity indices, bond lengths, and vibration frequencies of the reactive bonds. Our calculations do not involve adjustable parameters and uncover new patterns of reactivity. The generality of our model is demonstrated comparing the vibrationally adiabatic barriers obtained for 100 hydrogen-atom transfers with the corresponding experimental activation energies, after correction for the heat capacities of reactants and transition state. The rates of half of these reactions are calculated using the Transition-State Theory with the vibrationally adiabatic path of the Intersecting-State Model and the semiclassical correction for tunneling (ISM/scTST). The calculated rates are within an order of magnitude of the experimental ones at room temperature. The temperature dependencies and kinetic isotope effects of selected systems are also in good agreement with the available experimental data. Our model elucidates the roles of the reaction energy, electrophilicity, structural parameters, and tunneling in the reactivity of these systems and can be applied to make quantitative predictions for new systems. | URI: | https://hdl.handle.net/10316/10340 | ISSN: | 0002-7863 | DOI: | 10.1021/ja029298e | Direitos: | openAccess |
Aparece nas coleções: | FCTUC Química - Artigos em Revistas Internacionais |
Ficheiros deste registo:
Ficheiro | Descrição | Tamanho | Formato | |
---|---|---|---|---|
Absolute Rate Calculations for Atom Abstractions.pdf | 181.92 kB | Adobe PDF | Ver/Abrir |
Citações SCOPUSTM
28
Visto em 9/nov/2022
Citações WEB OF SCIENCETM
5
27
Visto em 2/set/2024
Visualizações de página
318
Visto em 1/out/2024
Downloads 50
506
Visto em 1/out/2024
Google ScholarTM
Verificar
Altmetric
Altmetric
Todos os registos no repositório estão protegidos por leis de copyright, com todos os direitos reservados.