%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 }