title: Testing for memory-free spectroscopic coordinates by 3D IR exchange spectroscopy.
abstract: Using 3D infrared (IR) exchange spectroscopy, the ultrafast hydrogen-bond forming and breaking (i.e., complexation) kinetics of phenol to benzene in a benzene/CCl4 mixture is investigated. By introducing a third time point at which the hydrogen-bonding state of phenol is measured (in comparison with 2D IR exchange spectroscopy), the spectroscopic method can serve as a critical test of whether the spectroscopic coordinate used to observe the exchange process is a memory-free, or Markovian, coordinate. For the system under investigation, the 3D IR results suggest that this is not the case. This conclusion is reconfirmed by accompanying molecular dynamics simulations, which furthermore reveal that the non-Markovian kinetics is caused by the heterogeneous structure of the mixed solvent.
authors.affiliation: Department of Chemistry, University of Zurich, CH-8057 Zurich, Switzerland.
authors.forename: Joanna A
authors.initials: JA
authors.lastname: Borek
authors.affiliation: Department of Chemistry, University of Zurich, CH-8057 Zurich, Switzerland.
authors.forename: Fivos
authors.initials: F
authors.lastname: Perakis
authors.affiliation: Department of Chemistry, University of Zurich, CH-8057 Zurich, Switzerland phamm@pci.uzh.ch.
authors.forename: Peter
authors.initials: P
authors.lastname: Hamm
keywords: 3D IR spectroscopy; solvent dynamics; ultrafast dynamics