Implementation of the Bethe−Salpeter equation in the TURBOMOLE program

Krause, Katharina; Klopper, Wim

doi:10.1002/jcc.24688

Cited by 108 publications

(124 citation statements)

References 42 publications

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“…For each excitation computed at the sTDA level, one can determine its natural transition orbitals (NTOs) and from those construct the corresponding transition density matrix [21,22] 1 as shown in Equation (12):…”

Section: Differential Many-body Expansion Of the Transition Densitymentioning

confidence: 99%

Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes

et al. 2015

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In computational chemistry, non-additive and cooperative effects can be defined in terms of a (differential) many-body expansion of the energy or any other physical property of the molecular system of interest. One-body terms describe energies or properties of the subsystems, two-body terms describe non-additive but pairwise contributions and three-body as well as higher-order terms can be interpreted as a measure for cooperativity. In the present article, this concept is applied to the analysis of ultraviolet/visible (UV/Vis) spectra of homotrinuclear transition-metal complexes by means of a many-body expansion of the change in the spectrum induced by replacing each of the three transition-metal ions by another transition-metal ion to yield a different homotrinuclear transition-metal complex. Computed spectra for the triangulo-complexes [M3 {Si(mt(Me) )3}2] (M=Pd/Pt, mt(Me) =methimazole) and tritopic triphenylene-based N-heterocyclic carbene Rh/Ir complexes illustrate the concept, showing large and small differential three-body cooperativity, respectively.

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Section: Differential Many-body Expansion Of the Transition Densitymentioning

confidence: 99%

Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes

et al. 2015

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“…[9][10][11][12][13][14][15][16][17][18][19][20][21] It now stands as a cost-effective computational method that can model excited states 22,23 with a typical error of 0.1-0.3 eV for spin-conserving transitions according to large and systematic benchmarks. [24][25][26][27][28][29][30] One of the main advantages of BSE compared to TD-DFT is that it allows a faithful description of charge-transfer states. [31][32][33][34][35][36] Moreover, when performed on top of a (partially) self-consistent evGW calculation, [37][38][39][40][41][42][43] BSE@evGW has been shown to be weakly dependent on its starting point (e.g., on the exchange-correlation functional selected for the underlying DFT calculation).…”

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confidence: 99%

Pros and Cons of the Bethe–Salpeter Formalism for Ground-State Energies

Loos

Scemama

Duchemin

et al. 2020

J. Phys. Chem. Lett.

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The combination of the many-body Green's function GW approximation and the Bethe-Salpeter equation (BSE) formalism has shown to be a promising alternative to time-dependent density-functional theory (TD-DFT) for computing vertical transition energies and oscillator strengths in molecular systems. The BSE formalism can also be employed to compute ground-state correlation energies thanks to the adiabatic-connection fluctuationdissipation theorem (ACFDT). Here, we study the topology of the ground-state potential energy surfaces (PES) of several diatomic molecules near their equilibrium bond length. Thanks to comparisons with state-of-art computational approaches (CC3), we show that ACFDT@BSE is surprisingly accurate, and can even compete with lower-order coupled cluster methods (CC2 and CCSD) in terms of total energies and equilibrium bond distances for the considered systems. However, we sometimes observe unphysical irregularities on the groundstate PES in relation with difficulties in the identification of a few GW quasiparticle energies.

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“…29 Finally, while proceeding technically as a perturbative correction based on input DFT Kohn–Sham eigenstates, which depend on the chosen exchange-correlation functional, the BSE results become (almost) independent of the selected starting point when adopting a (partially) self-consistent GW method, while conserving TD-DFT’s scaling and hence TD-DFT’s computational efficiency. 17 …”

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confidence: 99%

Is the Bethe–Salpeter Formalism Accurate for Excitation Energies? Comparisons with TD-DFT, CASPT2, and EOM-CCSD

Jacquemin

Duchemin

Blase

2017

J. Phys. Chem. Lett.

107

126

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Developing ab initio approaches able to provide accurate excited-state energies at a reasonable computational cost is one of the biggest challenges in theoretical chemistry. In that framework, the Bethe–Salpeter equation approach, combined with the GW exchange-correlation self-energy, which maintains the same scaling with system size as TD-DFT, has recently been the focus of a rapidly increasing number of applications in molecular chemistry. Using a recently proposed set encompassing excitation energies of many kinds [J. Phys. Chem. Lett.2016, 7, 586–591], we investigate here the performances of BSE/GW. We compare these results to CASPT2, EOM-CCSD, and TD-DFT data and show that BSE/GW provides an accuracy comparable to the two wave function methods. It is particularly remarkable that the BSE/GW is equally efficient for valence, Rydberg, and charge-transfer excitations. In contrast, it provides a poor description of triplet excited states, for which EOM-CCSD and CASPT2 clearly outperform BSE/GW. This contribution therefore supports the use of the Bethe–Salpeter approach for spin-conserving transitions.

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Implementation of the Bethe−Salpeter equation in the TURBOMOLE program

Cited by 108 publications

References 42 publications

Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes

Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes

Pros and Cons of the Bethe–Salpeter Formalism for Ground-State Energies

Is the Bethe–Salpeter Formalism Accurate for Excitation Energies? Comparisons with TD-DFT, CASPT2, and EOM-CCSD

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