Electronic Structure and Bonding of {Fe(PhNO2)}6 Complexes: 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: 2007, Том: 111, Номер: 18, Страницы: 3571-3576 Страниц : 6 DOI: 10.1021/jp0668798 | ||||
| Ключевые слова | Chemical bonds; Complexation; Degradation; Density functional theory; Electronic structure; Mathematical models | ||||
| Авторы |
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| Организации |
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Информация о финансировании (2)
| 1 | U.S. Army Engineer Research and Development Center | W912HZ-05-C-0051 |
| 2 | United States Army Research Laboratory | DAAD19-01-2-0014 |
Реферат:
Reduction of nitro-aromatic compounds (NACs) proceeds through intermediates with a partial electron transfer into the nitro group from a reducing agent. To estimate the extent of such a transfer and, therefore, the activity of various model ferrous-containing reductants toward NAC degradation, the unrestricted density functional theory (DFT) in the basis of paired Lo¨wdin-Amos-Hall orbitals has been applied to complexes of nitrobenzene (NB) and model Fe(II) hydroxides including cationic [FeOH]+, then neutral Fe(OH)2, and finally anionic [Fe(OH)3]-. Electron transfer is considered to be a process of unpairing electrons (without the change of total spin projection Sz) that reveals itself in a substantial spin contamination of the unrestricted solution. The unrestricted orbitals are transformed into localized paired orbitals to determine the orbital channels for a particular electron-transfer state and the weights of idealized charge-transfer and covalent electron structures. This approach allows insight into the electronic structure and bonding of the {Fe(PhNO2)}6 unit (according to Enemark and Feltham notation) to be gained using model nitrobenzene complexes. The electronic structure of this unit can be expressed in terms of π-type covalent bonding [Fe+2(d6, S ) 2) - PhNO2(S ) 0)] or charge-transfer configuration [Fe+3(d5, S ) 5/2) - {PhNO2}- ((π*)1, S ) 1/2)].
Библиографическая ссылка:
Isayev O.
, Gorb L.
, Zilberberg I.
, Leszczynski J.
Electronic Structure and Bonding of {Fe(PhNO2)}6 Complexes: A Density Functional Theory Study
The Journal of Physical Chemistry A. 2007. V.111. N18. P.3571-3576. DOI: 10.1021/jp0668798 WOS Scopus РИНЦ CAPlusCA OpenAlex
Electronic Structure and Bonding of {Fe(PhNO2)}6 Complexes: A Density Functional Theory Study
The Journal of Physical Chemistry A. 2007. V.111. N18. P.3571-3576. DOI: 10.1021/jp0668798 WOS Scopus РИНЦ CAPlusCA OpenAlex
Даты:
| Поступила в редакцию: | 19 окт. 2006 г. |
| Принята к публикации: | 31 янв. 2007 г. |
| Опубликована online: | 19 апр. 2007 г. |
| Опубликована в печати: | 1 мая 2007 г. |
Идентификаторы БД:
| Web of science: | WOS:000246189700020 |
| Scopus: | 2-s2.0-34249664859 |
| РИНЦ: | 13545211 |
| Chemical Abstracts: | 2007:427949 |
| Chemical Abstracts (print): | 147:126556 |
| OpenAlex: | W2054384451 |