Vibronic effects and destruction of exciton coherence in optical spectra of J-aggregates: A variational polaron transformation approachBloemsma, E. A., Silvis, M. H., Stradomska, A. & Knoester, J. 20-Dec-2016 In : Chemical Physics. 481, p. 250-261 12 p.
Research output: Scientific - peer-review › Article
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.
|Number of pages||12|
|State||Published - 20-Dec-2016|