Benchmarks for electronically excited states: Time-dependent density functional theory and density functional theory based multireference configuration interaction

Silva-Junior, Mario R.; Schreiber, Marko; Sauer, Stephan P. A.; Thiel, Walter

doi:doi:10.1063/1.2973541

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Isotropic non-Heisenberg terms in the magnetic coupling of transition metal complexes

This paper analyzes the different contributions to the magnetic coupling in systems with more than one unpaired electron per center. While in S = 1/2 spin systems the Heisenberg Hamiltonian involving only bilinear exchange interactions is reliable for the description of the magnetic states, biquadratic exchange interactions must be sometimes introduced for S = 1 (or higher) spin systems to account for isotropic deviations to Heisenberg behavior. The analysis establishes that the excited atomic ...

Quasiparticle energy spectra of alkali-metal clusters: All-electron first-principles calculations

A good approximation to the one-electron self-energy operator in the calculation of quasiparticle energy spectra including the first ionization potential (IP) and electron affinity (EA) is to expand it as a simple product of a one-particle Green’s function G and a dynamically screened Coulomb interaction W, namely, GW approximation. We developed a spin-polarized version of the all-electron GW approach and applied it to the first-principles calculation of quasiparticle energy spectra of alkali-m...

Time-dependent density functional theory (TD-DFT) and DFT-based multireference configuration interaction (DFT/MRCI) calculations are reported for a recently proposed benchmark set of 28 medium-sized organic molecules. Vertical excitation energies, oscillator strengths, and excited-state dipole moments are computed using the same geometries (MP2/6-31G^∗) and basis set (TZVP) as in our previous ab initio benchmark study on electronically excited states. The results from TD-DFT (with the functionals BP86, B3LYP, and BHLYP) and from DFT/MRCI are compared against the previous high-level ab initio results, and, in particular, against the proposed best estimates for 104 singlet and 63 triplet vertical excitation energies. The statistical evaluation for the latter reference data gives the lowest mean absolute deviations for DFT/MRCI (0.22 eV for singlets and 0.24 eV for triplets) followed by TD-DFT/B3LYP (0.27 and 0.44 eV, respectively), whereas TD-DFT/BP86 and TD-DFT/BHLYP are significantly less accurate. The energies of singlet states with double excitation character are generally overestimated by TD-DFT, whereas triplet state energies are systematically underestimated by the currently investigated DFT-based methods.

Article Outline

INTRODUCTION
COMPUTATIONAL METHODS
1. TD-DFT calculations
2. DFT/MRCI calculations
RESULTS AND DISCUSSION
1. Vertical excitation energies of the benchmark molecules
2. One-electron properties
3. Statistical evaluation
  1. Singlet state energies
  2. Triplet state energies
  3. Excited-state energy differences
  4. One-electron properties
SUMMARY

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KEYWORDS and PACS

Keywords

configuration interactions, density functional theory, molecular electronic states, molecular moments, organic compounds, oscillator strengths, perturbation theory, triplet state

PACS

31.15.ee

Time-dependent density functional theory
31.15.vj

Electron correlation calculations for atoms and ions: excited states
31.15.xp

Perturbation theory
33.15.Kr

Electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility
33.70.Ca

Oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.2973541

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

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$abstract.society.value is a Member of CrossRef

American Institute of Physics

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