Modeling the Gas-Phase Reduction of Nitrobenzene to Nitrosobenzene by Iron Monoxide: A Density Functional Theory Study Научная публикация
Журнал |
The Journal of Physical Chemistry A
ISSN: 1089-5639 , E-ISSN: 1520-5215 |
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Вых. Данные | Год: 2004, Том: 108, Номер: 22, Страницы: 4878-4886 Страниц : 9 DOI: 10.1021/jp037351v | ||||||
Ключевые слова | ELECTRONIC-STRUCTURE; CORRELATION-ENERGY; TRANSITION-METALS; OXYGEN MOLECULES; INFRARED-SPECTRA; FeO; ATOMS; THERMOCHEMISTRY; EXCHANGE; REPRESENTATION | ||||||
Авторы |
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Организации |
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Информация о финансировании (4)
1 | Совет по грантам Президента Российской Федерации | НШ-1140.2003.3 |
2 | Сибирское отделение Российской академии наук | 4.1.16 |
3 | United States Army Research Laboratory | DAAH04-95-2-0003/DAAH04-95-C-0008 |
4 | National Science Foundation | 300423-190200-21000 |
Реферат:
The gas-phase selective reduction of nitrobenzene (NB) to nitrosobenzene (NSB) by iron monoxide has been for the first time studied by means of density functional theory (DFT) using both the hybrid and pure exchange-correlation functionals. As shown at both DFT levels, when interacting with NB, the iron center donates an electron into the nitro group to form the NB- anion radical strongly coupled by FeO+. This electron-transfer characteristic of the NB-−FeO+ intermediate reveals itself in the S2 operator expectation value that exceeds its eigenvalue of S(S + 1) by almost 1.0. Further reaction steps necessary to obtain nitrosobenzene from this intermediate are discussed. One of the possible steps based on the abstraction of oxygen from the nitro group by a ferrous center is considered in detail. This reaction appears to be favorable at the pure DFT level, whereas the hybrid theory predicts small endothermicity for the process.
Библиографическая ссылка:
Zilberberg I.
, Ilchenko M.
, Isayev O.
, Gorb L.
, Leszczynski J.
Modeling the Gas-Phase Reduction of Nitrobenzene to Nitrosobenzene by Iron Monoxide: A Density Functional Theory Study
The Journal of Physical Chemistry A. 2004. V.108. N22. P.4878-4886. DOI: 10.1021/jp037351v WOS Scopus РИНЦ
Modeling the Gas-Phase Reduction of Nitrobenzene to Nitrosobenzene by Iron Monoxide: A Density Functional Theory Study
The Journal of Physical Chemistry A. 2004. V.108. N22. P.4878-4886. DOI: 10.1021/jp037351v WOS Scopus РИНЦ
Даты:
Поступила в редакцию: | 4 нояб. 2003 г. |
Принята к публикации: | 13 мар. 2004 г. |
Опубликована online: | 11 мая 2004 г. |
Опубликована в печати: | 1 июн. 2004 г. |
Идентификаторы БД:
Web of science | WOS:000221700100009 |
Scopus | 2-s2.0-2942704067 |
РИНЦ | 13450747 |
Chemical Abstracts | 2004:377224 |
Chemical Abstracts (print) | 141:106041 |
OpenAlex | W1984327540 |