On the origin of oscillations in two-dimensional spectra of excitonically-coupled molecular systems

Abstract

Weinvestigate an artificial molecular dimer made of two dipole coupled cyanine dye monomers in which a strong coherent coupling between electronic and vibrational degrees of freedom arises. Clear signatures of this coupling are reflected in an oscillatory time evolution of the off-diagonal vibronic cross peaks in the two-dimensional optical photon echo spectrum.Wefind a strong coherence component damped by fast electronic dephasing (≈50 fs) accompanied by amuchweaker component which decays on the longer time scales (ps) associated to vibrational dephasing.Wefind that vibronic coupling does not cause longer dephasing times of the dominant photo echo component but additional weak but long-lived components emerge.