Ultrafast Multidimensional Infrared Vibrational Echo Spectroscopy of Gases and Liquids
Author | : |
Publisher | : |
Total Pages | : 7 |
Release | : 2008 |
ISBN-10 | : OCLC:318693224 |
ISBN-13 | : |
Rating | : 4/5 (24 Downloads) |
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.