Volume 237, 2022

Signatures of coherent vibronic exciton dynamics and conformational control in the two-dimensional electronic spectroscopy of conjugated polymers

Abstract

Two-dimensional electronic spectroscopy (2DES) signals for homo-oligomer J-aggregates are computed, with a focus on the role of structural change induced by low-frequency torsional modes, along with quasi-stationary trapping effects induced by high-frequency polaronic modes. To this end, a model system is derived from an ab initio parametrized site-based Hamiltonian for oligothiophenes [Binder et al., Phys. Rev. Lett., 2018, 120, 227401]. To obtain a compact representation, we introduce a collective lattice mode whose vibronic coupling depends nonlinearly on the exciton density. As a result, an N-site model with a single polaronic mode and a single torsional mode is obtained. Furthermore, a quantum–classical treatment is employed where the torsional mode is treated within a mean-field Ehrenfest/Langevin approximation. 2D electronic spectra are computed using the equation-of-motion phase-matching approach (EOM-PMA) within a wavefunction description. It is seen that the spectra combine the vibronic fine structure, due to the polaronic mode, and a dynamic Stokes shift, due to torsional relaxation. The signatures of the coherent effects and adiabatic evolution in the 2DES signals are discussed.

Graphical abstract: Signatures of coherent vibronic exciton dynamics and conformational control in the two-dimensional electronic spectroscopy of conjugated polymers

Associated articles

Article information

Article type
Paper
Submitted
20 jan 2022
Accepted
22 fev 2022
First published
22 fev 2022

Faraday Discuss., 2022,237, 148-167

Signatures of coherent vibronic exciton dynamics and conformational control in the two-dimensional electronic spectroscopy of conjugated polymers

D. Brey, R. Binder, R. Martinazzo and I. Burghardt, Faraday Discuss., 2022, 237, 148 DOI: 10.1039/D2FD00014H

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