Bloemsma, E.A., Silvis, M.H., Stradomska, A. and Knoester, J. (2016) Vibronic effects and destruction of exciton coherence in optical spectra of J-aggregates: a variational polaron transformation approach. Chemical Physics, 481, pp. 250-261. (doi: 10.1016/j.chemphys.2016.06.018)
|
Text
120674.pdf - Accepted Version Available under License Creative Commons Attribution Non-commercial No Derivatives. 570kB |
Abstract
Using a symmetry adapted polaron transformation of the Holstein Hamiltonian, we study the interplay of electronic excitation-vibration couplings, resonance excitation transfer interactions, and temperature in the linear absorption spectra of molecular J-aggregates. Semi-analytical expressions for the spectra are derived and compared with results obtained from direct numerical diagonalization of the Hamiltonian in the two-particle basis set representation. At zero temperature, we show that our polaron transformation reproduces both the collective (exciton) and single-molecule (vibrational) optical response associated with the appropriate standard perturbation limits. Specifically, for the molecular dimer excellent agreement with the spectra from the two-particle approach for the entire range of model parameters is obtained. This is in marked contrast to commonly used polaron transformations. Upon increasing the temperature, the spectra show a transition from the collective to the individual molecular features, which results from the thermal destruction of the exciton coherence.
Item Type: | Articles |
---|---|
Additional Information: | A.S. acknowledges the Netherlands Organization for Scientific Research for support through a VENI grant. |
Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Stradomska-Szymczak, Dr Anna |
Authors: | Bloemsma, E.A., Silvis, M.H., Stradomska, A., and Knoester, J. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | Chemical Physics |
Publisher: | Elsevier |
ISSN: | 0301-0104 |
ISSN (Online): | 1873-4421 |
Published Online: | 02 July 2016 |
Copyright Holders: | Copyright © 2016 Elsevier B.V. |
First Published: | First published in Chemical Physics 481: 250-261 |
Publisher Policy: | Reproduced in accordance with the publisher copyright policy |
University Staff: Request a correction | Enlighten Editors: Update this record