Two dimensional infrared four wave mixing spectroscopy of simple molecules, peptides and proteins
Author(s)
Donaldson, Paul Murray
Type
Thesis
Abstract
In this thesis, measurements of electron-vibration-vibration two dimensional infrared
(EVV 2DIR) spectra are demonstrated for the first time from aliphatic, aromatic and
amide containing compounds. Bioanalytical applications of EVV 2DIR spectroscopy
are explored and the first EVV 2DIR measurements on proteins reported. Operational
protocols for collecting EVV 2DIR spectra are described and it is shown for the case of
benzene Fermi resonances how excitation pulse ordering can be used to isolate different
EVV coherence pathways, giving signals that report on several aspects of a molecule’s
electrical and mechanical anharmonicity. Experimental spectra are compared with first
principles simulations and in general found to be in good agreement with one another.
It is shown that inter-pulse delays can substantially clean up frequency domain spectra
and for the range of compounds studied, the 2DIR spectra are significantly decongested
compared with their 1D infrared and Raman counterparts. EVV 2DIR coherence
lifetime measurements are reported and applied to a range of simple organic
compounds. Measurements of exponential dephasing, nonexponential dephasing and
quantum beating are demonstrated, with the exponential decays used to accurately
measure vibrational linewidths and the quantum beats to measure line splittings.
(EVV 2DIR) spectra are demonstrated for the first time from aliphatic, aromatic and
amide containing compounds. Bioanalytical applications of EVV 2DIR spectroscopy
are explored and the first EVV 2DIR measurements on proteins reported. Operational
protocols for collecting EVV 2DIR spectra are described and it is shown for the case of
benzene Fermi resonances how excitation pulse ordering can be used to isolate different
EVV coherence pathways, giving signals that report on several aspects of a molecule’s
electrical and mechanical anharmonicity. Experimental spectra are compared with first
principles simulations and in general found to be in good agreement with one another.
It is shown that inter-pulse delays can substantially clean up frequency domain spectra
and for the range of compounds studied, the 2DIR spectra are significantly decongested
compared with their 1D infrared and Raman counterparts. EVV 2DIR coherence
lifetime measurements are reported and applied to a range of simple organic
compounds. Measurements of exponential dephasing, nonexponential dephasing and
quantum beating are demonstrated, with the exponential decays used to accurately
measure vibrational linewidths and the quantum beats to measure line splittings.
Date Issued
2008-04-01T12:51:43Z
Date Awarded
2008-03
Format Extent
17914759 bytes
Copyright Statement
Attribution NoDerivatives 4.0 International Licence (CC BY-ND)
Advisor
Klug, David
Creator
Donaldson, Paul Murray
Publisher Department
Chemistry
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)