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Title
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C-H bonds with a positive dipole gradient can form blue-shifting hydrogen bonds: the complex of halothane with methyl fluoride
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Author
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Abstract
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| The complex of halothane (CF3CBrClH) with ([D3])methyl fluoride is investigated theoretically by means of ab initio calculations at the MP2/6-311++G(d,p) level and experimentally by infrared spectroscopy of solutions in liquid krypton. The complexation energy is calculated to be -12.5 kJ mol-1. The dipole moment of halothane monomer as a function of the CH stretching coordinate is calculated with different methodologies and the value of (/Q1)0 is found to be positive. In the spectra, formation of a 1:1 complex is observed. The standard complexation enthalpy is measured to be -8.4(2) kJ mol-1. The CH stretching vibration of halothane shows a blueshift of +15.4 cm-1 on complexation, and its infrared intensity ratio complex/monomer is found to be 1.39(7). The frequency shift is analyzed by a Morokuma analysis, and the infrared intensities are rationalized by using a model which includes the mechanical and electrical anharmonicity of the CH stretching vibration. |
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Language
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English
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Source (journal)
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ChemPhysChem : a European journal of chemical physics and physical chemistry. - Weinheim, 2000 - 2015
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Publication
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Weinheim
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Wiley-VCH
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2008
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ISSN
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1439-4235
[print]
1439-7641
[online]
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DOI
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10.1002/CPHC.200800263
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Volume/pages
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9
:12
(2008)
, p. 1693-1701
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ISI
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000258851200006
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Full text (Publisher's DOI)
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