Spin-multiplet energies from time-dependent density functional theory

Petersilka, Martin; Gross, E. K. U.

doi:10.1002/(sici)1097-461x(1996)60:7<1393::aid-qua21>3.0.co;2-4

Cited by 47 publications

(39 citation statements)

References 36 publications

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“…In cases where there are large differences between SPA and full results, the SPA might be more reliable for these reasons. The fact that the corrections to the Kohn-Sham eigenvalue differences only weakly depend on the approximation of the exchange-correlation potential v xc , is also reflected in table 16, where the singlet-triplet separations in Be, calculated using the X-only KLI and OEP-SIC potentials are given. The numerical values are close to the results for the accurate Be exchange correlation potential in table 11.…”

Section: Approximate Kohn-sham Potentialsmentioning

confidence: 89%

Excitation Energies from Time-Dependent Density-Functional Theory

1996

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The role of the exchange-correlation potential and the exchange-correlation kernel in the calculation of excitation energies from time-dependent density functional theory is studied. Excitation energies of the helium and beryllium atoms are calculated, both from the exact Kohn-Sham ground-state potential, and from two orbital-dependent approximations. These are exact exchange and self-interaction corrected local density approximation (SIC-LDA), both calculated using Krieger-Li-Iafrate approximation. For the exchangecorrelation kernels, three adiabatic approximations were tested: the local density approximation, exact exchange, and SIC-LDA. The choice of the ground-state exchange correlation potential has the largest impact on the absolute position of most excitation energies. In particular, orbital-dependent approximate potentials result in a uniform shift of the transition energies to the Rydberg states.

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Section: Approximate Kohn-sham Potentialsmentioning

confidence: 89%

Excitation Energies from Time-Dependent Density-Functional Theory

1996

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“…Appendix A: Spin-adapted kernels For spin-restricted closed-shell calculations, spinsinglet and spin-triplet excitations can be decoupled [42][43][44] (see also Refs. 8,80).…”

Section: Acknowledgmentsmentioning

confidence: 99%

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

2013

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We study linear-response time-dependent density-functional theory (DFT) based on the singledeterminant range-separated hybrid (RSH) scheme, i.e. combining a long-range Hartree-Fock exchange kernel with a short-range DFT exchange-correlation kernel, for calculating electronic excitation 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 approximation (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 excitation 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 excitation 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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“…13,14 Perhaps the most popular application of time-dependent density functional theory (TD-DFT) in the molecular regime has been the calculation of excitation energies, in which many groups have, by now, been involved. 5,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] The equations from which the excitation energies are obtained are well-established. 18,20,25 They are formally quite similar to the time-dependent Hartree-Fock (TDHF) equations (TDHF is also known as random phase approximation (RPA)) and can be solved efficiently 25 by using iterative techniques, such as the Davidson algorithm.…”

Section: Introductionmentioning

confidence: 99%

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

et al. 1999

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The first time-dependent density functional theory (TDDFT) calculations on the spectra of molecules containing transition metals are reported. Three prototype systems are considered, of which the assignments are controversial: MnO 4 -, Ni(CO) 4 , and Mn 2 (CO) 10 . The TDDFT results are shown to be comparable in accuracy to the most elaborate ab initio calculations and lead to new insights in the spectra of these molecules. In some cases, the presented TDDFT results differ substantially, in both the ordering and the values for the excitation energies, from the older DFT method for the calculation of excitation energies: the ∆SCF approach. For the Mn 2 (CO) 10 molecule, the presented results are the highest-level theoretical results published so far. Over all, the results show that TDDFT can be a very useful tool in the calculation and interpretation of the spectra of transition metal compounds.

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Spin-multiplet energies from time-dependent density functional theory

Cited by 47 publications

References 36 publications

Excitation Energies from Time-Dependent Density-Functional Theory

Excitation Energies from Time-Dependent Density-Functional Theory

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

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

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Spin-multiplet energies from time-dependent density functional theory

Cited by 47 publications

References 36 publications

Excitation Energies from Time-Dependent Density-Functional Theory

Excitation Energies from Time-Dependent Density-Functional Theory

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

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO4-, Ni(CO)4, and Mn2(CO)10

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Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀