Multi-configuration time-dependent density-functional theory based on range separation

Abstract

Multi-configuration range-separated density-functional theory is extended to the time-dependent regime. An exact variational formulation is derived. The approximation, which consists in combining a long-range Multi-Configuration-Self-Consistent Field (MCSCF) treatment with an adiabatic short-range density-functional (DFT) description, is then considered. The resulting time-dependent multi-configuration short-range DFT (TD-MC-srDFT) model is applied to the calculation of singlet excitation energies in H2, Be and ferrocene, considering both short-range local density (srLDA) and generalized gradient (srGGA) approximations. In contrast to regular TD-DFT, TD-MC-srDFT can describe double excitations. As expected, when modeling long-range interactions with the MCSCF model instead of the adiabatic Buijse-Baerends density-matrix functional as recently proposed by Pernal [K. Pernal, J. Chem. Phys. 136, 184105 (2012)], the description of both the 1^1D doubly-excited state in Be and the 1^1Σ^+_u state in the stretched H2 molecule are improved, although the latter is still significantly underestimated. Exploratory TD-MC-srDFT/GGA calculations for ferrocene yield in general excitation energies at least as good as TD-DFT/CAM-B3LYP, and superior to wave-function (TD-MCSCF, symmetry adapted cluster-configuration interaction) and TD-DFT results based on LDA, GGA, and hybrid functionals.

41 pages, 4 figures, 2 tables

References in corpus (13)

• Perspective on density functional theory
• Fundamental gaps of finite systems from the eigenvalues of a generalized Kohn-Sham method
• Long-range/short-range separation of the electron-electron interaction in density functional theory
• Van der Waals forces in density functional theory: perturbational long-range electron interaction corrections
• Adiabatic-connection fluctuation-dissipation density-functional theory based on range separation
• Perspectives on double-excitations in TDDFT
• Long-range-corrected hybrids including RPA correlation
• Local-spin-density functional for multideterminant density functional theory
• Excitonic optical spectrum of semiconductors obtained by time-dependent density-functional theory with the exact-exchange kernel
• Multi-configuration time-dependent density-functional theory based on range separation
• On the "Causality Paradox" of Time-Dependent Density Functional Theory
• Range separation combined with the Overhauser model: Application to the H${}_2$ molecule along the dissociation curve
• Comment on "Modifying the variational principle in the action integral functional derivation of time-dependent density functional theory" by Jochen Schirmer [arXiv:1010.4223]

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