Successes and failures of time-dependent density functional theory for the low-lying excited states of chlorophylls Export

@article{citeulike:1865977, abstract = {It has been suggested that electronic excited states outside of those included within the Gouterman four-orbital model (<i>Q</i><i>_y</i>, <i>Q</i><i>_x</i>, <i>B</i><i>_x</i>, and <i>B</i><i>_y</i>) are present in the low-energy region of chlorophyll molecules. In particular, studies performed using time-dependent density functional theory (TDDFT) predict the presence of a very large number of such states, most of whom are expected to be \&lsquo;dark\&rsquo; states that are thus difficult to identify. So far, there has been no experimental test that has authoritatively confirmed or contradicted these predictions. The paper considers the response of the TDDFT-calculated excited states to applied electric fields of the order of those experienced by the chlorophylls in Photosystem-I (PS-I). TDDFT calculations using the PW91 density functional with the 6-31G* basis set are shown to predict that charge-transfer bands form the lowest excited state under these conditions, contrary to experimental results. In general, TDDFT calculations using modern functionals are shown to be unreliable for calculations of the excited states of chlorophylls, although important, realistic spectral information is depicted within them that may possibly be extracted for useful purposes.}, author = {Dahlbom, Mats G. and Reimers, Jeffrey R.}, citeulike-article-id = {1865977}, citeulike-linkout-0 = {http://dx.doi.org/10.1080/00268970412331333528}, doi = {10.1080/00268970412331333528}, journal = {Molecular Physics}, keywords = {chlorophyll, td-dft}, number = {6}, pages = {1057--1065}, posted-at = {2009-11-05 21:48:57}, priority = {2}, publisher = {Taylor \&amp; Francis}, title = {Successes and failures of time-dependent density functional theory for the low-lying excited states of chlorophylls}, url = {http://dx.doi.org/10.1080/00268970412331333528}, volume = {103}, year = {2005} }

TY - JOUR ID - citeulike:1865977 L3 - citeulike-article-id:1865977 N2 - It has been suggested that electronic excited states outside of those included within the Gouterman four-orbital model (<i>Q</i><i>_y</i>, <i>Q</i><i>_x</i>, <i>B</i><i>_x</i>, and <i>B</i><i>_y</i>) are present in the low-energy region of chlorophyll molecules. In particular, studies performed using time-dependent density functional theory (TDDFT) predict the presence of a very large number of such states, most of whom are expected to be &lsquo;dark&rsquo; states that are thus difficult to identify. So far, there has been no experimental test that has authoritatively confirmed or contradicted these predictions. The paper considers the response of the TDDFT-calculated excited states to applied electric fields of the order of those experienced by the chlorophylls in Photosystem-I (PS-I). TDDFT calculations using the PW91 density functional with the 6-31G* basis set are shown to predict that charge-transfer bands form the lowest excited state under these conditions, contrary to experimental results. In general, TDDFT calculations using modern functionals are shown to be unreliable for calculations of the excited states of chlorophylls, although important, realistic spectral information is depicted within them that may possibly be extracted for useful purposes. IS - 6 JF - Molecular Physics EP - 1065 TI - Successes and failures of time-dependent density functional theory for the low-lying excited states of chlorophylls PB - Taylor &amp; Francis VL - 103 SP - 1057 KW - chlorophyll KW - td-dft AU - Dahlbom, Mats AU - Reimers, Jeffrey PY - 2005/// UR - http://dx.doi.org/10.1080/00268970412331333528 ER -