Send to

Choose Destination
See comment in PubMed Commons below
J Chem Phys. 2006 Aug 28;125(8):084502.

Characterization of spectral diffusion from two-dimensional line shapes.

Author information

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.


The analysis of line shapes in two-dimensional optical and infrared spectroscopies is a powerful approach to characterizing the dynamics of molecules in the condensed phase. Changes in line shape from diagonally elongated to symmetric as a function of waiting time arise from evolution of the transition frequency. We describe a number of quantitative measures of frequency fluctuations and spectral diffusion through the analysis of two-dimensional (2D) line shapes. These metrics are identical to the system's frequency correlation function and independent of population relaxation in the limit of a short time approximation for the 2D response. We also test the broader applicability of these expressions for analyzing three-level vibrational systems and experiments with finite pulses.

PubMed Commons home

PubMed Commons

How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for American Institute of Physics
    Loading ...
    Support Center