Title
A cryosolution FTIR and ab initio study of the blue shifting <tex>$C-H\cdots F$</tex> hydrogen bonded complexes <tex>$F_{2}ClCH\cdot FCD_{3}$</tex> and <tex>$Cl_{2}FCH\cdot FCD_{3}$</tex> A cryosolution FTIR and ab initio study of the blue shifting <tex>$C-H\cdots F$</tex> hydrogen bonded complexes <tex>$F_{2}ClCH\cdot FCD_{3}$</tex> and <tex>$Cl_{2}FCH\cdot FCD_{3}$</tex>
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
Amsterdam ,
Subject
Physics
Chemistry
Source (journal)
Chemical physics. - Amsterdam
Volume/pages
354(2008) , p. 71-79
ISSN
0301-0104
ISI
000261980100009
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
The mid (4000500 cm−1) and near (10,0004000 cm−1) infrared spectra of solutions in liquid krypton containing mixtures of F2ClCH and FCD3 or of Cl2FCH and FCD3 show the formation of 1:1 complexes. MP2/6-311++G(2d, 2p) ab initio calculations suggest that the main interaction responsible for the formation of the complexes is the hydrogen bond between the haloform CH bond and the fluorine atom of the base molecule. The observation of blue shifts upon complexation of 24.8, 51.5 and 87 cm−1 for the fundamental, the first and the second overtone of the haloform í1 in F2ClCH, and of 25.0, 50.2 and 87 cm−1 in Cl2FCH show that in either case the hydrogen bond is of the blue-shifting type. Upon complexation the intensity of the fundamental í1 in F2ClCH decreases by a factor of approximately 5, while that in Cl2FCH increases, by a factor of approximately 4. At the same time, the intensities of the first and second overtones reveal only modest decreases. The MP2/6-311++G(2d, 2p) calculations predict the existence of more than one conformer for either complex. No spectral evidence for conformational equilibria in the complexes has been detected. One-dimensional anharmonic model calculations have been made to simulate the blue shift and intensity behaviour of the haloform í1 vibrations. For both complexes these calculations reproduce the experimental data with reasonable success.
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