Assessment of Dressed Time-Dependent Density-Functional Theory for the Low-Lying Valence States of 28 Organic Chromophores

Chemical Physics 391, 120 - 129 (2011)

Assessment of Dressed Time-Dependent Density-Functional Theory for the Low-Lying Valence States of 28 Organic Chromophores

Miquel Huix-Rotllant, Andrei Ipatov, Angel Rubio, Mark Casida

Almost all time-dependent density-functional theory (TDDFT) calculations of excited states make use of the adiabatic approximation, which implies a frequency-independent exchangecorrelation kernel that limits applications to one-hole/one-particle states. To remedy this problem, Maitra et al.[J.Chem.Phys. 120, 5932 (2004)] proposed dressed TDDFT (D-TDDFT), which includes explicit two-hole/two-particle states by adding a frequency-dependent term to adiabatic TDDFT. This paper offers the first extensive test of D-TDDFT, and its ability to represent excitation energies in a general fashion. We present D-TDDFT excited states for 28 chromophores and compare them with the benchmark results of Schreiber et al.[J.Chem.Phys. 128, 134110 (2008).] We find the choice of functional used for the A-TDDFT step to be critical for positioning the 1h1p states with respect to the 2h2p states. We observe that D-TDDFT without HF exchange increases the error in excitations already underestimated by A-TDDFT. This problem is largely remedied by implementation of D-TDDFT including Hartree-Fock exchange.

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http://dx.doi.org/doi:10.1016/j.chemphys.2011.03.019
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http://www.sciencedirect.com/science/article/pii/S0301010411000954

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