title: Linear and third- and fifth-order nonlinear spectroscopies of a charge transfer system coupled to an underdamped vibration.
abstract: We study hole, electron, and exciton transports in a charge transfer system in the presence of underdamped vibrational motion. We analyze the signature of these processes in the linear and third-, and fifth-order nonlinear electronic spectra. Calculations are performed with a numerically exact hierarchical equations of motion method for an underdamped Brownian oscillator spectral density. We find that combining electron, hole, and exciton transfers can lead to non-trivial spectra with more structure than with excitonic coupling alone. Traces taken during the waiting time of a two-dimensional (2D) spectrum are dominated by vibrational motion and do not reflect the electron, hole, and exciton dynamics directly. We find that the fifth-order nonlinear response is particularly sensitive to the charge transfer process. While third-order 2D spectroscopy detects the correlation between two coherences, fifth-order 2D spectroscopy (2D population spectroscopy) is here designed to detect correlations between the excited states during two different time periods.
authors.affiliation: Max Planck Institute for the Structure and Dynamics of Matter, Hamburg, Germany.
authors.forename: Arend G
authors.initials: AG
authors.lastname: Dijkstra
authors.affiliation: Department of Chemistry, Kyoto University, Kyoto, Japan.
authors.forename: Yoshitaka
authors.initials: Y
authors.lastname: Tanimura
mesh_terms: D004579:Electron Transport; D017711:Nonlinear Dynamics; D011789:Quantum Theory; D013057:Spectrum Analysis; D014732:Vibration