Ab initio Calculation of Nitrogen Oxide Dimer Structure and Its Anion-Radical Научная публикация
| Журнал |
Journal of Structural Chemistry
ISSN: 0022-4766 , E-ISSN: 1573-8779 |
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| Вых. Данные | Год: 2005, Том: 46, Номер: 2, Страницы: 213-219 Страниц : 7 DOI: 10.1007/s10947-006-0033-1 | ||||
| Ключевые слова | Ab initio method, Complex with copper cation, Density functional theory, Nitrogen oxide dimer | ||||
| Авторы |
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| Организации |
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Информация о финансировании (1)
| 1 | Совет по грантам Президента Российской Федерации | НШ-1140.2003.3 |
Реферат:
A comparative quantum chemical analysis has been made for the most stable dimer of nitrogen oxide with the structure cis-ONNO in a singlet state 1 A 1 by ab initio method of SCF MO LCAO, allowing for electron correlation according to Meller-Plesset perturbation theory of the second order (MP2), and density functional technique (DFT). The computations by MP2 method show anion-radical (ONNO)− to have a strong bond between nitrogen atoms (N-N 1.44 Å) in contrast to molecular weakly bound cis-dimer with equilibrium distance N-N 2.23 Å. Molecular orbital structure of the dimer and its anions was examined that made it possible to suggest a reason of preferable stabilization of nitrogen oxide dimer in the cis-form. Calculated high affinity to electron (E a = −1.55-−1.69 eV) for the molecular dimer ONNO (1 A 1) explains an intense strengthening of N-N bond in anion-radical and confirms the experimental data on a possibility of surface anion-π-radical formation on electron donor centers. The DFT computations indicate that this technique poorly reproduces the experimental geometry and electron structure of the cis-dimer ONNO having predicted a triplet ground state with the equilibrium distance N-N ≈2 Å instead of a singlet one with N-N 2.26 Å. The comparison between MP2 and DFT calculations for complex dimer ONNO with copper cation reveals the energy state of the complex (Cu-O2N2)+ corresponding to stabilization of anion-π-radical (N2O2)− {term-3 A 2, Cu(d)9-(ONNO)−1} to be highly overestimated by DFT.
Библиографическая ссылка:
Zakharov I.I.
, Anufrienko V.F.
, Zakharova O.I.
, Yashnik S.A.
, Ismagilov Z.R.
Ab initio Calculation of Nitrogen Oxide Dimer Structure and Its Anion-Radical
Journal of Structural Chemistry. 2005. V.46. N2. P.213-219. DOI: 10.1007/s10947-006-0033-1 WOS Scopus РИНЦ CAPlusCA OpenAlex
Ab initio Calculation of Nitrogen Oxide Dimer Structure and Its Anion-Radical
Journal of Structural Chemistry. 2005. V.46. N2. P.213-219. DOI: 10.1007/s10947-006-0033-1 WOS Scopus РИНЦ CAPlusCA OpenAlex
Оригинальная:
Захаров И.И.
, Ануфриенко В.Ф.
, Захарова О.И.
, Яшник С.А.
, Исмагилов З.Р.
Неэмпирический расчет структуры димера оксида азота и его анион-радикала
Журнал структурной химии. 2005. Т.46. №2. С.221-227. РИНЦ
Неэмпирический расчет структуры димера оксида азота и его анион-радикала
Журнал структурной химии. 2005. Т.46. №2. С.221-227. РИНЦ
Даты:
| Поступила в редакцию: | 15 мар. 2004 г. |
| Опубликована в печати: | 1 мар. 2005 г. |
Идентификаторы БД:
| Web of science: | WOS:000237701800003 |
| Scopus: | 2-s2.0-33744986696 |
| РИНЦ: | 13474283 |
| Chemical Abstracts: | 2006:545257 |
| Chemical Abstracts (print): | 145:404636 |
| OpenAlex: | W1995892424 |