Double excitations in finite systems

Romaniello, Pina; Sangalli, Davide; Berger, J. A.; Sottile, Francesco; Molinari, Luca; Reining, Lucia; Onida, Giovanni

doi:10.1063/1.3065669

Cited by 117 publications

(135 citation statements)

References 48 publications

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“…16−21 Over the past 20 years, the TDDFT approach has become the workhorse in DFT-based studies of excited states, and its strengths and weaknesses are well documented. 22 −37 On the other hand, progress beyond the adiabatic approximation has been slow, although work in this direction is ongoing. 38−40 TDDFT has the distinct advantage over ΔSCF that it can deal with states that are multideterminantal.…”

Section: Introductionmentioning

confidence: 98%

Applications of Time-Dependent and Time-Independent Density Functional Theory to Electronic Transitions in Tetrahedral d⁰ Metal Oxides

Seidu

Krykunov

Ziegler

2015

J. Chem. Theory Comput.

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We present benchmark calculations on excitation energies based on time-dependent density functional theory (TDDFT) as well as orbital relaxed self-consistent and constricted variational DFT (RSCF-CV-DFT) with and without use of the Tamm-Dancoff approximation. The compilation contains results for the 3d complexes MnO₄⁻, CrO₄²⁻, and VO₄³⁻, as well as the 4d congeners RuO₄, TcO₄⁻, and MoO₄²⁻, and 5d homologues OsO₄, ReO₄⁻, and WO₄²⁻. Considerations have been given to the local density approximation (LDA) and the functionals BP86 and PBE based on the generalized gradient approximation (GGA), as well as the hybrids B3LYP, BHLYP, and PBE0 and the length corrected functional LCBP86. We find for the 3d complexes that RSCF-CV-DFT fares better than TDDFT. Thus, in the case of RSCF-CV-DFT, the average root-mean-square deviations (RMSDs) are 0.25-0.3 eV for GGAs, 0.1 eV for B3LYP, and 0.45 eV for BHLYP. TDDFT affords RMSDs that on average range from 0.3 eV for local functionals to 0.7 eV for BHLYP with the largest fraction of Hartree-Fock (HF) exchange. TDDFT is seen to fare better among the heavier tetraoxo systems. For the 4d and 5d systems, the three functionals B3LYP, PBE0 with an intermediate fraction of HF exchange, and LCBP86 have the lowest RMSD of 0.2 eV, whereas the local functionals (LDA, BP86, BPE) and BHLYP with the highest HF fraction and LCBP86* have a somewhat larger RMSD of 0.3 eV. Nearly the same performance is observed for RSCF-CV-DFT with respect to the different functionals in the case of the 4d and 5d systems. Thus, for the heavier tetraoxo systems, the two DFT schemes are comparable in accuracy.

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Section: Introductionmentioning

confidence: 98%

Applications of Time-Dependent and Time-Independent Density Functional Theory to Electronic Transitions in Tetrahedral d⁰ Metal Oxides

Seidu

Krykunov

Ziegler

2015

J. Chem. Theory Comput.

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“…Recent work has demonstrated that higher excitations only arise in the above theories with the retention of a frequency dependent interaction kernel. 46,47 Specifically, one solves the eigenvalue-like equation, H(ω)c = ωc, with…”

Section: Aside Regarding Wavefunction Free Methodsmentioning

confidence: 99%

Microscopic theory of singlet exciton fission. I. General formulation

Berkelbach¹,

Hybertsen²,

Reichman³

2013

The Journal of Chemical Physics

253

415

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Singlet fission, a spin-allowed energy transfer process generating two triplet excitons from one singlet exciton, has the potential to dramatically increase the efficiency of organic solar cells. However, the dynamical mechanism of this phenomenon is not fully understood and a complete, microscopic theory of singlet fission is lacking. In this work, we assemble the components of a comprehensive microscopic theory of singlet fission that connects excited state quantum chemistry calculations with finite-temperature quantum relaxation theory. We elaborate on the distinction between localized diabatic and delocalized adiabatic bases for the interpretation of singlet fission experiments in both the time and frequency domains. We discuss various approximations to the exact density matrix dynamics and propose Redfield theory as an ideal compromise between speed and accuracy for the detailed investigation of singlet fission in dimers, clusters, and crystals. Investigations of small model systems based on parameters typical of singlet fission demonstrate the numerical accuracy and practical utility of this approach.

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“…62,66,70,78,80 Frequency-dependent exchange-correlation kernels have been proposed recently and tested on model systems. 81,82 …”

Section: B Restricted Excitation Window Tddftmentioning

confidence: 99%

Core and valence excitations in resonant X-ray spectroscopy using restricted excitation window time-dependent density functional theory

Zhang

Biggs

Healion

et al. 2012

The Journal of Chemical Physics

107

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We report simulations of X-ray absorption near edge structure (XANES), resonant inelastic X-ray scattering (RIXS) and 1D stimulated X-ray Raman spectroscopy (SXRS) signals of cysteine at the oxygen, nitrogen, and sulfur K and L 2,3 edges. Comparison of the simulated XANES signals with experiment shows that the restricted window time-dependent density functional theory is more accurate and computationally less expensive than the static exchange method. Simulated RIXS and 1D SXRS signals give some insights into the correlation of different excitations in the molecule.

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Double excitations in finite systems

Cited by 117 publications

References 48 publications

Applications of Time-Dependent and Time-Independent Density Functional Theory to Electronic Transitions in Tetrahedral d⁰ Metal Oxides

Applications of Time-Dependent and Time-Independent Density Functional Theory to Electronic Transitions in Tetrahedral d⁰ Metal Oxides

Microscopic theory of singlet exciton fission. I. General formulation

Core and valence excitations in resonant X-ray spectroscopy using restricted excitation window time-dependent density functional theory

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Double excitations in finite systems

Cited by 117 publications

References 48 publications

Applications of Time-Dependent and Time-Independent Density Functional Theory to Electronic Transitions in Tetrahedral d0 Metal Oxides

Applications of Time-Dependent and Time-Independent Density Functional Theory to Electronic Transitions in Tetrahedral d0 Metal Oxides

Microscopic theory of singlet exciton fission. I. General formulation

Core and valence excitations in resonant X-ray spectroscopy using restricted excitation window time-dependent density functional theory

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Product

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Applications of Time-Dependent and Time-Independent Density Functional Theory to Electronic Transitions in Tetrahedral d⁰ Metal Oxides

Applications of Time-Dependent and Time-Independent Density Functional Theory to Electronic Transitions in Tetrahedral d⁰ Metal Oxides