skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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:
 [1];  [2]
  1. Max Planck Institute for the Structure and Dynamics of Matter, Hamburg (Germany)
  2. Department of Chemistry, Kyoto University, Kyoto (Japan)
Publication Date:
OSTI Identifier:
22415898
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 21; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; CORRELATIONS; COUPLING; ELECTRON SPECTRA; ELECTRON SPECTROSCOPY; ELECTRONS; EQUATIONS OF MOTION; EXCITED STATES; EXCITONS; HOLES; NONLINEAR PROBLEMS; OSCILLATORS; SPECTRAL DENSITY; TWO-DIMENSIONAL SYSTEMS

Citation Formats

Dijkstra, Arend G., E-mail: arend.dijkstra@mpsd.mpg.de, E-mail: tanimura@kuchem.kyoto-u.ac.jp, and Tanimura, Yoshitaka, E-mail: arend.dijkstra@mpsd.mpg.de, E-mail: tanimura@kuchem.kyoto-u.ac.jp. Linear and third- and fifth-order nonlinear spectroscopies of a charge transfer system coupled to an underdamped vibration. United States: N. p., 2015. Web. doi:10.1063/1.4917025.
Dijkstra, Arend G., E-mail: arend.dijkstra@mpsd.mpg.de, E-mail: tanimura@kuchem.kyoto-u.ac.jp, & Tanimura, Yoshitaka, E-mail: arend.dijkstra@mpsd.mpg.de, E-mail: tanimura@kuchem.kyoto-u.ac.jp. Linear and third- and fifth-order nonlinear spectroscopies of a charge transfer system coupled to an underdamped vibration. United States. doi:10.1063/1.4917025.
Dijkstra, Arend G., E-mail: arend.dijkstra@mpsd.mpg.de, E-mail: tanimura@kuchem.kyoto-u.ac.jp, and Tanimura, Yoshitaka, E-mail: arend.dijkstra@mpsd.mpg.de, E-mail: tanimura@kuchem.kyoto-u.ac.jp. 2015. "Linear and third- and fifth-order nonlinear spectroscopies of a charge transfer system coupled to an underdamped vibration". United States. doi:10.1063/1.4917025.
@article{osti_22415898,
title = {Linear and third- and fifth-order nonlinear spectroscopies of a charge transfer system coupled to an underdamped vibration},
author = {Dijkstra, Arend G., E-mail: arend.dijkstra@mpsd.mpg.de, E-mail: tanimura@kuchem.kyoto-u.ac.jp and Tanimura, Yoshitaka, E-mail: arend.dijkstra@mpsd.mpg.de, E-mail: tanimura@kuchem.kyoto-u.ac.jp},
abstractNote = {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.},
doi = {10.1063/1.4917025},
journal = {Journal of Chemical Physics},
number = 21,
volume = 142,
place = {United States},
year = 2015,
month = 6
}
  • The cascading polarization contributing to the femtosecond fifth- and seventh-order coherent Raman scattering processes is obtained in terms of the third- and fifth-order Raman response functions. It is found that four cascading processes contribute to the fifth-order Raman scattering signal. In the case of the seventh-order Raman scattering, there are 34 possible cascading processes contributing to the seventh-order Raman scattering signal, and they are classified as {chi}{sup (5)}x{chi}{sup (3)}- and {chi}{sup (3)}x{chi}{sup (3)}x{chi}{sup (3)}-types depending on the involved low-order nonlinear optical processes. Due to the complicated interference among these polarization fields, it may not be possible to experimentally measure themore » pure seventh-order Raman scattering signal without contamination from the cascaded contributions. (c) 2000 American Institute of Physics.« less
  • The third-order nonlinear optical response of energy transfer systems is theoretically investigated. A system composed of two chromophores having the same electronic transition energies is considered. The dynamics of energy transfer between the two chromophores is assumed to occur via a hopping (incoherent) mechanism. We introduce new types of pathways incorporating the hopping processes occurring while the system is in population states and reconstruct a third-order response function which is computationally viable. The nuclear propagators in the electronic population states are written as convolution integrals between those of the nonreactive two-state system weighted by some factors for the energy transfer.more » The response function is given by multitime correlation functions and these are analyzed by the cumulant expansion method. Based on this approach, the three-pulse photon echo peak shift for several models of energy transfer systems is discussed. It is shown that the rephasing capability of the induced signal is reduced by the memory loss due to resonant energy transfer. A previous model which incorporates resonant energy transfers in an intuitive way is reviewed and modified to supplement the loss of dynamic correlation of nuclear motion within the framework of the theory. The response function obtained by our new approach gives a more accurate description than the existing theory and a comparative discussion is given. The effect of inhomogeneity in rate constants on the third-order signal is discussed and the temperature dependence of the echo signal is examined. {copyright} {ital 1999 American Institute of Physics.}« less
  • The signals generated by various third-order nonlinear spectroscopies (transient absorption, transient grating, and three-pulse photon echo peak shift) on energy transfer systems are investigated by carrying out model calculations. Focusing on the understanding of basic features, we employ a simple model system consisting of pairs of energy donors and acceptors. We assume that energy transfer occurs via the Foerster mechanism (weak electronic coupling). Static disorder in the transition energies of the chromophores induces inhomogeneities in the rate of energy transfer and in the optical response. The interplay between these two processes is discussed. We show that the peak shift experimentmore » has advantages over the other types of experiment in clarifying the nature of disorder which affects the mechanism and time scale of energy transfer. For example, the peak shift technique can reveal the extent to which disorder is correlated in individual chromophore assemblies, and the extent to which energy transfer can correlate the energies of donors and acceptors. Finally the ability of the peak shift method to distinguish and quantify diagonal and off-diagonal disorder in energy transfer systems is discussed. (c) 2000 American Institute of Physics.« less
  • A third-order nonlinear theory, neglecting thermal distribution and collisions of the plasma electrons, is developed for a longitudinal, one- dimensional beam--plasma system. A study is made of the saturation of the fundamental at large input levels. The input level at which the fundamental current density would reach maximum is found for a typical practical situation. (auth)
  • We have demonstrated that fifth-order stimulated Raman spectra of the intermolecular modes in CS{sub 2} are dominated by cascading third-order processes. Previous studies have successfully discriminated against a sequential cascading process, but did not account for parallel third-order cascades. All of our measured spectra were successfully simulated considering only cascades built directly from our measured third-order spectra. Using an appropriately chosen phase matching geometry we also measured the sequential cascade, which should exist with equal probability to the parallel cascade. When employing a phase matching geometry that provided substantial discrimination against all of the third-order cascades we were not ablemore » to measure any signal. We assign an upper limit for the true fifth-order signal of 2{percent} of the cascaded signal. {copyright} {ital 1999 American Institute of Physics. }« less