Title:
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High resolution laser and infrared spectroscopy and ab initio calculations for the study of intermolecular hydrogen bonding
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A blue shift in the CH stretching vibration of formic acid cyclic dimer of 6.6 ern"
(symmetric) and 3 ern" (antisymmetric) is observed by high resolution Raman
(symmetric) and infrared (antisymmetric) spectroscopy. This is corroborated by
theoretical ab initio calculations where blue shifts in the CH stretching vibration of
12.79 ern" (symmetric) and 10.26 ern" (antisymmetric) are calculated
(CP corrected MP2/6-311++G(d,p) level of theory). This is unusual due to the CH
bond not playing a direct part in the bonding of the dimer.
The electric dipole moment derivative curve with respect to bond length of the CH
bond in formic acid is found to be unusual. The equilibrium bond length is on the
negative gradient side of the maximum of the dipole, and this has been used to
explain interesting behaviour observed, including the blue shift of the CH
stretching vibration and how the contribution of electrostatics to the interaction
energy can cause a blue shift of the stretching vibration in the spectrum.
A mechanism is proposed where the electron density is transferred from the CH
bond, through to the OH site where bonding does take place. This in turn causes
the CH bond to have increased polarity, and therefore the bond contracts due to
this interaction.
Several chloroform complexes are investigated, which show either blue shifting or
red shifting of the CH stretching vibration. Complexation with dimethyl ether
shows an experimental red shift of the CH stretching vibration of chloroform of
-1.5 ern", and a theoretical shift of -2.11 crn'. The complex of chloroform with
trimethyl amine shows an experimental red shift of the CH stretching vibration of
chloroform of -54 ern", and a theoretical prediction of -79.51 ern". Both of these
complexes show a 1: 1 stoichiometric equation. The chloroform self dimer shows
blue shifts in the CH stretching vibration, calculated to be 2.1 and 8.8 ern",
experimental results are currently inconclusive.
Morokuma Kitaura energy decomposition has been used to understand the energy
contributions to intermolecular bonding. Electrostatic interaction and exchange
repulsion have been shown to be the main contributions to bonding, but some
unusual cases, for example the CH bond of formic acid cyclic dimer, have shown
electrostatics to cause a blue shift.
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A tuneable stimulated Raman photoacoustic spectroscopy (PARS) set up has been
further applied to the trace detection of H2' and has achieved a detection limit of
6.69 ppm by volume. A non-dispersive Raman shifter method has also been
investigated as a simpler alternative to the tuneable PARS set up and has
achieved a less sensitive detection limit of 108 ppm by volume. Methane has also
been detected qualitatively via this method, using the Raman shifter as a source
of infrared light.
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