We theoretically study the two-dimensional (2D) spectroscopy of molecular dimers. The spectra are first analyzed within an electronic level model. It is demonstrated how the angular average over molecular orientations influences the features of the spectra. Methods to calculate angular averaged vibronic spectra within perturbation theory are compared. We systematically document changes in the 2D-spectra upon going from homo- to heterodimers. In particular, it is demonstrated that large-amplitude off-diagonal peaks appear for heterodimers even in the limit of vanishing coupling. This is related to the difference in the excitation energies of the two different monomers. For homodimers with equal monomer excitation energies, such peaks become diagonal peaks and thus cannot be isolated.
Description
Two-dimensional optical spectroscopy of homo- and heterodimers - Physical Chemistry Chemical Physics (RSC Publishing)
%0 Journal Article
%1 C6CP04936B
%A Wehner, Johannes
%A Engel, Volker
%D 2016
%I The Royal Society of Chemistry
%J Phys. Chem. Chem. Phys.
%K ak-engel myown
%N 48
%P 32910-32920
%R 10.1039/C6CP04936B
%T Two-dimensional optical spectroscopy of homo- and heterodimers
%U http://dx.doi.org/10.1039/C6CP04936B
%V 18
%X We theoretically study the two-dimensional (2D) spectroscopy of molecular dimers. The spectra are first analyzed within an electronic level model. It is demonstrated how the angular average over molecular orientations influences the features of the spectra. Methods to calculate angular averaged vibronic spectra within perturbation theory are compared. We systematically document changes in the 2D-spectra upon going from homo- to heterodimers. In particular, it is demonstrated that large-amplitude off-diagonal peaks appear for heterodimers even in the limit of vanishing coupling. This is related to the difference in the excitation energies of the two different monomers. For homodimers with equal monomer excitation energies, such peaks become diagonal peaks and thus cannot be isolated.
@article{C6CP04936B,
abstract = {We theoretically study the two-dimensional (2D) spectroscopy of molecular dimers. The spectra are first analyzed within an electronic level model. It is demonstrated how the angular average over molecular orientations influences the features of the spectra. Methods to calculate angular averaged vibronic spectra within perturbation theory are compared. We systematically document changes in the 2D-spectra upon going from homo- to heterodimers. In particular{,} it is demonstrated that large-amplitude off-diagonal peaks appear for heterodimers even in the limit of vanishing coupling. This is related to the difference in the excitation energies of the two different monomers. For homodimers with equal monomer excitation energies{,} such peaks become diagonal peaks and thus cannot be isolated.},
added-at = {2017-06-20T16:34:52.000+0200},
author = {Wehner, Johannes and Engel, Volker},
biburl = {https://www.bibsonomy.org/bibtex/24de89cfab7c9da360f221bb25e797c3b/ak-engel-uniwue},
description = {Two-dimensional optical spectroscopy of homo- and heterodimers - Physical Chemistry Chemical Physics (RSC Publishing)},
doi = {10.1039/C6CP04936B},
interhash = {98c3d123fcccf0f817c100411e52edd3},
intrahash = {4de89cfab7c9da360f221bb25e797c3b},
journal = {Phys. Chem. Chem. Phys.},
keywords = {ak-engel myown},
number = 48,
pages = {32910-32920},
publisher = {The Royal Society of Chemistry},
timestamp = {2017-06-21T08:12:42.000+0200},
title = {Two-dimensional optical spectroscopy of homo- and heterodimers},
url = {http://dx.doi.org/10.1039/C6CP04936B},
volume = 18,
year = 2016
}