Accession Number:

ADA488161

Title:

Ultrafast Multidimensional Infrared Vibrational Echo Spectroscopy of Gases and Liquids

Descriptive Note:

Final rept. 12 Jan 2004-30 Nov 2007

Corporate Author:

STANFORD UNIV CA

Personal Author(s):

Report Date:

2008-09-17

Pagination or Media Count:

7.0

Abstract:

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.

Subject Categories:

  • Physical Chemistry
  • Atomic and Molecular Physics and Spectroscopy

Distribution Statement:

APPROVED FOR PUBLIC RELEASE