Open AccessVerdict: Time-Dependent Density Functional Theory “Not Guilty” of Large Errors for Cyanines
Author(s) -
Denis Jacquemin,
Yan Zhao,
Rosendo Valero,
Carlo Adamo,
Ilaria Ciofini,
Donald G. Truhlar
Publication year - 2012
Publication title -
journal of chemical theory and computation
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.001
H-Index - 185
eISSN - 1549-9626
pISSN - 1549-9618
DOI - 10.1021/ct200721d
Subject(s) - cyanine , time dependent density functional theory , density functional theory , excitation , quantum , statistical physics , physics , computational chemistry , chemistry , quantum mechanics , fluorescence
We assess the accuracy of eight Minnesota density functionals (M05 through M08-SO) and two others (PBE and PBE0) for the prediction of electronic excitation energies of a family of four cyanine dyes. We find that time-dependent density functional theory (TDDFT) with the five most recent of these functionals (from M06-HF through M08-SO) is able to predict excitation energies for cyanine dyes within 0.10-0.36 eV accuracy with respect to the most accurate available Quantum Monte Carlo calculations, providing a comparable accuracy to the latest generation of CASPT2 calculations, which have errors of 0.16-0.34 eV. Therefore previous conclusions that TDDFT cannot treat cyanine dyes reasonably accurately must be revised.