Ultrafast excited-state isomerization dynamics of 1,1'-diethyl-2,2'-cyanine studied by four-wave mixing spectroscopy.
Excited-state dynamics and solvent-solute interactions of 1,1'-diethyl-2,2'-cyanine iodine (1122C) in alcoholic solutions are investigated using time-integrated three-pulse photon-echo spectroscopy. 1122C serves as a model compound for ultrafast photoinduced isomerization-a key process in the light reception of plants, bacteria, and human vision. The photoreaction in 1122C is interrogated in dependence on solvent and excitation wavelength. The wavelength-dependent three-pulse photon-echo peak shift indicates strong alterations of the reaction pathways and points to the existence of a direct internal conversion channel in close proximity to the Franck-Condon point of absorption. The solvent-dependent S1-S0 internal conversion time does not follow conventional sheared viscosity dependence, suggesting that the solvent local friction has to be considered to account for the observed isomerization kinetics. The concerted discussion of transient grating and three-pulse photon-echo peak-shift data allows us to derive a complete picture of the solvent-solute interaction-controlled photoreaction. The results obtained are related to other work on reactive systems and are discussed in the framework of multilevel response functions.
Dietzek
Benjamin
B
Department of Chemical Physics, Lund University, P. O. Box 124, SE-22100 Lund, Sweden. dietzek@mit.edu
Christensson
Niklas
N
Pascher
Torbjörn
T
Pullerits
Tõnu
T
Yartsev
Arkady
A