title: Solvation beyond the linear response regime.
abstract: Transient two-dimensional infrared spectroscopy (2D-IR) on a charge transfer model system is used as a nonlinear probe of solvation dynamics. Unlike what is expected in the linear response case, nonequilibrium relaxation and equilibrium spectral diffusion occur on different time scales. Transient 2D-IR spectroscopy is shown to be sensitive to higher order frequency fluctuation correlation functions, and provides evidence for a coupling between commonly observed fast and slow solvation processes.
authors.affiliation: Physikalisch-Chemisches Institut, Universität Zürich, Winterthurerstr. 190, CH-8057 Zürich, Switzerland.
authors.forename: Jens
authors.initials: J
authors.lastname: Bredenbeck
authors.forename: Jan
authors.initials: J
authors.lastname: Helbing
authors.forename: Peter
authors.initials: P
authors.lastname: Hamm