The integrated photon echo and solvation dynamics. II. Peak shifts and two-dimensional photon echo of a coupled chromophore system.
A theoretical description of one- and two-color photon echo peak shifts (PEPS) and two-dimensional (2D) photon echo spectrum (PES) of a coupled chromophore system are presented. The effects of population relaxation in the one-exciton states on both the PEPS and the 2D PES are investigated. For values of time T shorter than the population relaxation time, a finite two-color peak shift magnitude and nonzero cross peaks in the 2D PES provide evidence of electronic coupling between the chromophores. These two distinct observables, i.e., PEPS and off-diagonal peaks, both originate from the electronic coupling. However, it is shown that the PEPS and 2D PES methods can provide complementary information on the structure-dependent nonlinear optical responses of coupled chromophore systems.
Cho
Minhaeng
M
Department of Chemistry and Center for Multidimensional Spectroscopy, Division of Chemistry and Molecular Engineering, Korea University, Seoul, Korea.
Fleming
Graham R
GR
D000465:Algorithms; D003198:Computer Simulation; D005456:Fluorescent Dyes / Q000737:chemistry* / Q000528:radiation effects; D008163:Luminescent Measurements / Q000379:methods*; D008956:Models, Chemical; D008958:Models, Molecular; D010777:Photochemistry / Q000379:methods*; D017785:Photons
D005456:Fluorescent Dyes