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. © 2011 Elsevier B.V. All rights reserved.This work has been carried out in the context of the French Rhône-Alpes Réseau thématique de recherche avancée (RTRA): Nanosciences aux limites de la nanoélectronique and the Rhône-Alpes Associated Node of the European Theoretical Spectroscopy Facility (ETSF). A. R. acknowledges funding by the Spanish MEC (FIS2007-65702-C02-01), ACI-promciona project (ACI2009-1036), “Grupos Consolidados UPV/EHU del Gobierno Vasco” (IT-319-07), the European Research Council through the advance grant DYNamo (267374), the MICINN project (FIS2010-21282-C02-01), and the European Community through projects e-I3 ETSF (Contract No. 211956) and THEMA (228539).Peer Reviewe