Title
Cryospectroscopic and **ab initio** studies of haloformtrimethylamine H-bonded complexes
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
Cambridge ,
Subject
Physics
Chemistry
Source (journal)
Physical chemistry, chemical physics / Royal Society of Chemistry. - Cambridge, 1999, currens
Volume/pages
11(2009) :10 , p. 1551-1563
ISSN
1463-9076
1463-9084
ISI
000263837200010
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
The FTIR spectra of F2ClCH and Cl3CH(D) in mixtures with trimethylamine (TMA) have been studied in liquefied Kr in 8004000 cm-1 frequency range. Spectroscopic evidence of a medium strength H-bond formation with conventional features has been found between these weak CH proton donors and TMA. The relative stability of the complexes has been determined in a series of temperature (T = 118157 K) measurements of integrated intensities of vibrational bands ascribed to monomer and complex species. The complexes found are characterized by the red shift of the 1(CH) stretching vibration of the haloforms studied. In the case of chloroform, the substantial red shift is accompanied by a noticeable broadening effect and by a marked growth of the intensity of this band. The spectroscopic changes caused by the complex formation have been also registered for vibrations of TMA. Specifically, the bands situated in the frequency domain of CH stretching vibrations of TMA show a weak blue shift, whereas the NC stretching vibrations are red-shifted. Ab initio MP2/6-311++G(2d,2p) a priori counterpoise corrected calculations, made for a series of haloforms and TMA, reproduce the main spectroscopic observations. The results obtained also suggest that the vibrational mode coupling between vicinal CH and CB (B = Hal, N) bonds is to a great extent responsible for the sign of these bond length changes and for the sign of the frequency shifts of the respective stretching vibrations upon complex formation.
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