Ultrafast Multidimensional Infrared Vibrational Echo Spectroscopy of Gases and Liquids

Download or read book Ultrafast Multidimensional Infrared Vibrational Echo Spectroscopy of Gases and Liquids written by and published by . This book was released on 2008 with total page 7 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.