Ultrafast Multidimensional Infrared Vibrational Echo Spectroscopy of Gases and Liquids
Final rept. 12 Jan 2004-30 Nov 2007
STANFORD UNIV CA
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Ultrafast infrared 2D-IR vibrational echo experiments were extended experimentally and theoretically. Detailed studies of water dynamics were performed and compared to MD simulations. 2D-IR vibrational echo chemical exchange experiments were used to study the formation and dissociation kinetics of eight solute-solvent complexes, and the results were related to the enthalpies of formation. MD simulations of the chemical exchange were performed for the phenol-benzene complex and found to be in good agreement with the data. Chemical exchange experiments were used to measure the rate of gauche-trans orientational isomerization about a carbon-carbon single bond. The dynamics of molecules in the first solvation shell of solutes in mixed solvents were studied, and the time dependent solvent compositional fluctuations about solutes were elucidated. A detailed time dependent diagrammatic perturbation theory of the 2D-IR vibrational echo chemical exchange experiment including spectral diffusion, orientational relaxation, and vibrational relaxation was developed. An important new theoretical method for determining the dynamics from 2D-IR vibrational echo experiments was developed and demonstrated.
- Physical Chemistry
- Atomic and Molecular Physics and Spectroscopy