The Davydov or exciton splitting of vertical excitation energies is commonly used to estimate the excitation energy transfer rate between chromophores. Here we investigate the S1?S2 Davydov splitting in 2-pyridone dimer as a function of the monomer separation, R. We assess the ability of various functionals to reproduce the Davydov splitting at finite R predicted by the approximate coupled cluster singles doubles method CC2. While semilocal functionals fail qualitatively because of spurious charge-transfer intruder states, global hybrids with a large fraction of exact exchange, such as BHandH-LYP, reproduce the CC2 splittings within few wavenumbers. We analyze our results by comparison to lowest-order intermolecular perturbation theory in the spirit of Fo?rster and Dexter. At equilibrium hydrogen bond distance, the Fo?rster?Dexter splittings are too small by up to a factor of 2.
%0 Journal Article
%1 AK26
%A Sagvolden, Espen
%A Furche, Filipp
%A Köhn, Andreas
%D 2009
%J J. Chem. Theory Comput.
%K chemie imported koehn köhn from:alexanderdenzel theoretische stuttgart theochem
%N 4
%P 873–880
%R 10.1021/ct800551g
%T Förster energy transfer and davydov splittings in time-dependent density functional theory: lessons from 2-pyridone dimer
%U http://dx.doi.org/10.1021/ct800551g
%V 5
%X The Davydov or exciton splitting of vertical excitation energies is commonly used to estimate the excitation energy transfer rate between chromophores. Here we investigate the S1?S2 Davydov splitting in 2-pyridone dimer as a function of the monomer separation, R. We assess the ability of various functionals to reproduce the Davydov splitting at finite R predicted by the approximate coupled cluster singles doubles method CC2. While semilocal functionals fail qualitatively because of spurious charge-transfer intruder states, global hybrids with a large fraction of exact exchange, such as BHandH-LYP, reproduce the CC2 splittings within few wavenumbers. We analyze our results by comparison to lowest-order intermolecular perturbation theory in the spirit of Fo?rster and Dexter. At equilibrium hydrogen bond distance, the Fo?rster?Dexter splittings are too small by up to a factor of 2.
%@ 1549-9618
@article{AK26,
abstract = {The Davydov or exciton splitting of vertical excitation energies is commonly used to estimate the excitation energy transfer rate between chromophores. Here we investigate the S1?S2 Davydov splitting in 2-pyridone dimer as a function of the monomer separation, R. We assess the ability of various functionals to reproduce the Davydov splitting at finite R predicted by the approximate coupled cluster singles doubles method CC2. While semilocal functionals fail qualitatively because of spurious charge-transfer intruder states, global hybrids with a large fraction of exact exchange, such as BHandH-LYP, reproduce the CC2 splittings within few wavenumbers. We analyze our results by comparison to lowest-order intermolecular perturbation theory in the spirit of Fo?rster and Dexter. At equilibrium hydrogen bond distance, the Fo?rster?Dexter splittings are too small by up to a factor of 2.},
added-at = {2019-02-06T13:16:24.000+0100},
author = {Sagvolden, Espen and Furche, Filipp and K{\"{o}}hn, Andreas},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/25c51525b66a5e7e68b0914d64d42ccd8/theochem},
doi = {10.1021/ct800551g},
interhash = {2e9b3fe3c757ad9493e70f5a8e91225c},
intrahash = {5c51525b66a5e7e68b0914d64d42ccd8},
isbn = {1549-9618},
issn = {15499618},
journal = {J. Chem. Theory Comput.},
keywords = {chemie imported koehn köhn from:alexanderdenzel theoretische stuttgart theochem},
number = 4,
pages = {873–880},
timestamp = {2019-02-06T12:16:24.000+0100},
title = {{F{\"{o}}rster energy transfer and davydov splittings in time-dependent density functional theory: lessons from 2-pyridone dimer}},
url = {http://dx.doi.org/10.1021/ct800551g},
volume = 5,
year = 2009
}