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Intermolecular interactions between halothane and dimethyl ether: a cryosolution infrared and ab initio study
- Source :
- ChemPhysChem: a European journal of chemical physics and physical chemistry
- Publication Year :
- 2007
-
Abstract
- The complex of halothane (CHClBrCF(3)) and dimethyl ether has been investigated experimentally in solutions of liquid krypton using infrared spectroscopy and theoretically using ab initio calculations at the MP2/6-311++G(d,p) level. The formation of a 1:1 complex was experimentally detected. The most stable ab initio geometry found is the one in which the C--H bond of halothane interacts with the oxygen atom of dimethyl ether. The complexes in which the chlorine or the bromine atom of halothane interacts with the oxygen atom of the ether were found to be local energy minima and were less stable by 14.5 and 9.3 kJ mol(-1), respectively, than the global minimum. The formation of a single complex species was observed in the infrared spectra; the standard complexation enthalpy of this complex was determined to be -12.3(8) kJ mol(-1). Analysis of the observed complexation shifts supports the identification of the complex as the hydrogen-bonded species. The C--H stretching vibration of halothane was found to show a redshift upon complexation of 19(2) cm(-1). The infrared intensity ratios epsilon(complex)/epsilon(monomer) for the fundamental and its first overtone were measured to be 6.5(1) and 0.31(1). The frequency shift was analyzed using Morokuma-type analysis, and the infrared intensity ratios were rationalized using a model including the mechanical and electric anharmonicity of the C--H stretching fundamental.
- Subjects :
- Methyl Ethers
Models, Molecular
Molecular Structure
Spectrophotometry, Infrared
Hydrogen bond
Infrared
Intermolecular force
Ab initio
Infrared spectroscopy
Ether
Vibration
Atomic and Molecular Physics, and Optics
chemistry.chemical_compound
chemistry
Isomerism
Models, Chemical
Ab initio quantum chemistry methods
Computational chemistry
Physical chemistry
Thermodynamics
Dimethyl ether
Physical and Theoretical Chemistry
Halothane
Subjects
Details
- Language :
- English
- ISSN :
- 14394235
- Database :
- OpenAIRE
- Journal :
- ChemPhysChem: a European journal of chemical physics and physical chemistry
- Accession number :
- edsair.doi.dedup.....291111228a11f66caf86fa690be41038