Assessment of dressed time-dependent density-functional theory for the low-lying valence states of 28 organic chromophores |
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Authors: | Miquel Huix-Rotllant Andrei IpatovAngel Rubio Mark E Casida |
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Institution: | a Laboratoire de Chimie Théorique, Département de Chimie Molécularie (DCM, UMR CNRS/UJF 5250), Institut de Chimie Moléculaire de Grenoble (ICMG, FR2607), Université Joseph Fourier (Grenoble I), 301 rue de la Chimie, BP 53, F-38041 Grenoble Cedex 9, France b Nano-Bio Spectroscopy Group and ETSF Scientific Development Centre, Departamento de Física de Materiales, Universidad del Pa?´s Vasco, E-20018 San Sebastián, Spain c Centro de Física de Materiales CSIC-UPV/EHU-MPC and DIPC, E-20018 San Sebastián, Spain d Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin-Dahlem, Germany |
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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. |
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Keywords: | Time-dependent density-functional theory Exchange-correlation kernel Adiabatic approximation Frequency dependence Many-body perturbation theory Excited states Organic chromophores |
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