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Journal Articles Molecular Physics Year : 2013

Electronic excitations from a linear- response range-separated hybrid scheme

Elisa Rebolini
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Julien Toulouse

Abstract

We study linear-response time-dependent density-functional theory (DFT) based on the single- determinant range-separated hybrid (RSH) scheme, i.e. combining a long-range Hartree-Fock ex- change kernel with a short-range DFT exchange-correlation kernel, for calculating electronic excita- tion energies of molecular systems. It is an alternative to the more common long-range correction (LC) scheme which combines a long-range Hartree-Fock exchange kernel with a short-range DFT exchange kernel and a standard full-range DFT correlation kernel. We discuss the local-density ap- proximation (LDA) to the short-range exchange and correlation kernels, and assess the performance of the linear-response RSH scheme for singlet → singlet and singlet → triplet valence and Rydberg excitations in the N2 , CO, H2CO, C2H4 , and C6H6 molecules, and for the first charge-transfer ex- citation in the C2H4-C2F4 dimer. For these systems, the presence of long-range LDA correlation in the ground-state calculation and in the linear-response kernel has only a small impact on the excita- tion energies and oscillator strengths, so that the RSH method gives results very similar to the ones given by the LC scheme. Like in the LC scheme, the introduction of long-range HF exchange in the present method corrects the underestimation of charge-transfer and high-lying Rydberg excitation energies obtained with standard (semi)local density-functional approximations, but also leads to underestimated excitation energies to low-lying spin-triplet valence states. This latter problem is largely cured by the Tamm-Dancoff approximation which leads to a relatively uniform accuracy for all excitation energies. This work thus suggests that the present linear-response RSH scheme is a reasonable starting approximation for describing electronic excitation energies, even before adding an explicit treatment of long-range correlation.
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Dates and versions

hal-00808223 , version 1 (05-04-2013)

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  • HAL Id : hal-00808223 , version 1

Cite

Elisa Rebolini, Andreas Savin, Julien Toulouse. Electronic excitations from a linear- response range-separated hybrid scheme. Molecular Physics, 2013, 111 (9-11), pp.10.1080/00268976.2013.794313. ⟨hal-00808223⟩
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