Title
C-H bonds with a positive dipole gradient can form blue-shifting hydrogen bonds: the complex of halothane with methyl fluoride
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
Weinheim ,
Subject
Physics
Chemistry
Source (journal)
ChemPhysChem: a European journal of chemical physics and physical chemistry. - Weinheim
ChemPhysChem: a European journal of chemical physics and physical chemistry. - Weinheim
Volume/pages
9(2008) :12 , p. 1693-1701
ISSN
1439-4235
ISI
000258851200006
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
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.
E-info
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