РАСЧЕТ ИК СПЕКТРОВ АРИЛ(АЛКИЛ) ХЛОРФОСФАТОВ В ПРИБЛИЖЕНИИ DFT
Електронний архів E-archive DonNTU – (Electronic archive Donetsk National Technical University)
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| Title |
РАСЧЕТ ИК СПЕКТРОВ АРИЛ(АЛКИЛ) ХЛОРФОСФАТОВ В ПРИБЛИЖЕНИИ DFT
DFT CALCULATION OF THE IR SPECTRA OF THE ARYL (ALKYL) CHLORPHOSPHATES |
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| Creator |
Анищенко, Виктор Николаевич
Рыбаченко, Владимир Иванович Чотий, Константин Юрьевич Редько, Андрей Николаевич |
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| Subject |
PBE0
PED хлорфосфаты ИК DFT PBE0 PED chlorphosphates IR |
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| Description |
Рассчитаны ИК спектры хлорангидридов фосфорных кислот методом DFT PBE0/6-31G(2df,p). На основании распределения потенциальной энергии (PED) выполнено полное отнесение частот экспериментальных ИК спектров для дихлорметил- и дихлорфенил-фосфата. Установлено, что при отнесении частот требуется учет всех стабильных конформеров изученных молекул.
The IR spectra of chlorphosphates were calculated using NWChem-6.1 software at the DFT level of theory with PBE0/6-31G(2df,p) method. Conformational analysis of chlorophosphate was performed in three stages with gradual increasing of the level of theory (from molecular mechanic to DFT). After each step, doubles were removed. Different conformations are the consequence of the rotation O–R fragment in relation to the P=O bond. In result was shown that dichlorophosphates are mixtures of three rotamers with +synclinal, -synclinal (±sc), and antiperiplanar (ap) arrangement. For complete assignment of experimentally registered vibrational frequencies of methyl- and phenyl- dichlorphosphates was used potential energy distribution (PED). It is showed that in frequencies assigning requires consideration of all the stable conformers of the studied molecules. The spatial arrangement of the organic substituents most pronounced in the fingerprint region of infrared spectrum - (1400 - 400 cm-1). IR spectrum of a mixture of conformers was obtained as a superposition of the IR spectra of the individual conformers. The use of non-empirical PBE0 functional in combination with the basis set 6-31G (2df, p) allowed to achieve a good agreement between the calculated and experimental IR spectra. |
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| Date |
2013-04-13T13:10:41Z
2013-04-13T13:10:41Z 2013 |
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| Type |
Article
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| Identifier |
2074-6652
http://ea.donntu.edu.ua/handle/123456789/18466 |
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| Relation |
Наукові праці ДонНТУ.;Серія: Хімія і хімічна технологія, 2013. - Вип.2(21). - С.92-96
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| Publisher |
Донецк, ДонНТУ
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