Absorption and Circular Dichroism Spectra of Molecular Aggregates With the Full Cumulant Expansion
Name
jp0c05180.pdf
Description
Published version
Size
1.26 MB
Format
Adobe PDF
Checksum (MD5)
4ded871c1112970d038b9d875c47717d
Author(s)
Cupellini, Lorenzo
Lipparini, Filippo
Cao, Jianshu
Date Issued
2020
Journal
Journal of Physical Chemistry B
Publisher
American Chemical Society (ACS)
Citation
Cupellini, Lorenzo, Lipparini, Filippo and Cao, Jianshu. 2020. "Absorption and Circular Dichroism Spectra of Molecular Aggregates With the Full Cumulant Expansion." Journal of Physical Chemistry B, 124 (39).
Version
Final published version
Abstract
Copyright © 2020 American Chemical Society. The exciton Hamiltonian of multichromophoric aggregates can be probed by spectroscopic techniques such as linear absorption and circular dichroism. To compare calculated Hamiltonians to experiments, a lineshape theory is needed, which takes into account the coupling of the excitons with inter- and intramolecular vibrations. This coupling is normally introduced in a perturbative way through the cumulant expansion formalism and further approximated by assuming a Markovian exciton dynamics, for example with the modified Redfield theory. Here, we present the implementation of the full cumulant expansion (FCE) formalism (J. Chem. Phys. 142, 2015, 094106) to efficiently compute absorption and circular dichroism spectra of molecular aggregates beyond the Markov approximation, without restrictions on the form of exciton-phonon coupling. By employing the LH2 system of purple bacteria as a challenging test case, we compare the FCE lineshapes with the Markovian lineshapes obtained with the modified Redfield theory, showing that the latter presents a less satisfying agreement with experiments. The FCE approach instead accurately describes the lineshapes, especially in the vibronic sideband of the B800 peak. We envision that the FCE approach will become a valuable tool for accurately comparing model exciton Hamiltonians with optical spectroscopy experiments.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Creative Commons Attribution 4.0 International license
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/ACS.JPCB.0C05180
