Квантово-химическое моделированиЕ ЯМР 1Н и 13С спектров гидропероксида 1,1,3-триметил-3-(4-метилфенил)бутила
Електронний архів E-archive DonNTU – (Electronic archive Donetsk National Technical University)
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| Title |
Квантово-химическое моделированиЕ ЯМР 1Н и 13С спектров гидропероксида 1,1,3-триметил-3-(4-метилфенил)бутила
QUANTUM CHEMICAL MODELING OF THE 1,1,3-TRIMETHYL-3-(4-METHYL-PHENYL)BUTYL HYDROPEROXIDE NMR 1H AND 13C SPECTRA |
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| Creator |
Ракша, Е.В.
Берестнева, Ю.В. Туровский, Н.А. Зубрицкий, М.Ю. |
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| Subject |
гидропероксиды
ЯМР 1Н и 13С спектроскопия молекулярное моделирование hydroperoxides NMR 1H and 13C spectroscopy molecular modeling |
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| Description |
Molecular modeling of the peroxide bond homolytic cleavage and association processes of hydroperoxides is an additional source of information about the structural effects that accompany these reactions. One of the criteria for the selection of quantum chemical methods to study the hydroperoxides reactivity is a reproduction with sufficient accuracy of the NMR 1H and 13C spectra. Calculations of nuclear shieldings of the 1,1,3-trimethyl-3 - (4-methylphenyl)butyl hydroperoxide were performed by the GIAO method at various computational levels, including the density functional theory with the hybrid functional B3LYP and second order Muller-Plesset perturbation theory (MP2) with the 6-31G(d,p) basis set. All calculations were performed using the GAUSSIAN 03 software package. The chemical shift values (δ, ppm) of the 1H and 13C nuclei in the hydroperoxide molecule were evaluated on the basis of calculated magnetic shielding constants. Tetramethylsilane (TMS) was used as a standard. The chemical shifts values of 1H and 13C found as the difference of the magnetic shielding constants of the corresponding nuclei TMS and hydroperoxide.The comparison of the calculated and experimental solution data was carried out focusing on the agreement with spectral patterns and spectral trends. The best reproduction of experimental values was obtained by MP2/6-31G(d,p) method with the non-specific solvation accounting in the framework of the polarization continuum model.
В рамках теории функционала плотности с использованием гибридного функционала B3LYP и теории возмущений Мюллера-Плессета второго порядка (МР2) с базисным набором 6-31G(d,p) методом GIAO рассчитаны химические сдвиги ядер 1Н и 13С гидропероксида 1,1,3-триметил-3-(4-метилфенил)бутила. Выполнено сопоставление рассчитанных и экспериментальных величин. Наилучшее воспроизведение экспериментальных величин получено методом МР2/6-31G(d,p) с учетом неспецифической сольватации в рамках модели поляризационного континиума. |
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| Date |
2014-04-15T14:49:50Z
2014-04-15T14:49:50Z 2014 |
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| Type |
Article
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| Identifier |
УДК 544.176:547-39
http://ea.donntu.edu.ua/handle/123456789/25984 |
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| Language |
other
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| Publisher |
Наукові праці ДонНТУ. Серія: Хімія і хімічна технологія. - 2014. - Вип. 1(22). - С. 150-156
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