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Assessment of dressed time-dependent density-functional theory for the low-lying valence states of 28 organic chromophores

Abstract : Almost all time-dependent density-functional theory (TDDFT) calculations of excited states make use of the adiabatic approximation, which implies a frequency-independent exchange-correlation kernel that limits applications to one-hole/ one-particle states. To remedy this problem, Maitra et al. [N. T. Maitra, F. Zhang, R. J. Cave, K. Burke, Double excitations within time-dependent density functional theory linear response theory, J. Chem. Phys. 120 (2004) 5932] 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. [M. Schreiber, M. R. Silva-Junior, S. P. A. Sauer, W. Thiel, Benchmarks for electronically excited states: CASPT2, CC2, CCSD, and CC3, J. Chem. Phys. 128 (2008) 134110]. 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. (C) 2011 Elsevier B. V. All rights reserved.
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Submitted on : Monday, December 12, 2016 - 6:50:13 PM
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Miquel Huix-Rotllant, Andrei Ipatov, Angel Rubio, Mark E. Casida. Assessment of dressed time-dependent density-functional theory for the low-lying valence states of 28 organic chromophores. Chemical Physics, Elsevier, 2011, 391 (1), pp.120--129. ⟨10.1016/j.chemphys.2011.03.019⟩. ⟨hal-01415195⟩

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