Length dependence of ionization potentials of transacetylenes: Internally consistent DFT/<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>G</mml:mi><mml:mi>W</mml:mi></mml:mrow></mml:math>approach

Pinheiro, Max; Caldas, M. J.; Rinke, Patrick; Blüm, Volker; Scheffler, Matthias

doi:10.1103/physrevb.92.195134

Cited by 33 publications

(44 citation statements)

References 87 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…In this approach, α is determined by requiring that the self-energy correction to the HOMO level within the G 0 W 0 approximation [11] is minimized. Eventually, this also fixes the starting point dependence of the perturbative GW approximation [12][13][14]. the local exchange potential in the PBE approximation [6].…”

Section: Introductionmentioning

confidence: 90%

Enforcing the linear behavior of the total energy with hybrid functionals: Implications for charge transfer, interaction energies, and the random-phase approximation

et al. 2016

Self Cite

View full text Add to dashboard Cite

We obtain the exchange parameter of hybrid functionals by imposing the fundamental condition of a piecewise linear total energy with respect to electron number. For the Perdew-Burke-Ernzerhof (PBE) hybrid family of exchange-correlation functionals (i.e., for an approximate generalized Kohn-Sham theory) this implies that (i) the highest occupied molecular orbital corresponds to the ionization potential (I ), (ii) the energy of the lowest unoccupied molecular orbital corresponds to the electron affinity (A), and (iii) the energies of the frontier orbitals are constant as a function of their occupation. In agreement with a previous study [N. Sai et al., Phys. Rev. Lett. 106, 226403 (2011)], we find that these conditions are met for high values of the exact exchange admixture α and illustrate their importance for the tetrathiafulvalene-tetracyanoquinodimethane complex for which standard density functional theory functionals predict artificial electron transfer. We further assess the performance for atomization energies and weak interaction energies. We find that atomization energies are significantly underestimated compared to PBE or PBE0, whereas the description of weak interaction energies improves significantly if a 1/R 6 van der Waals correction scheme is employed.

show abstract

Section: Introductionmentioning

confidence: 90%

Enforcing the linear behavior of the total energy with hybrid functionals: Implications for charge transfer, interaction energies, and the random-phase approximation

et al. 2016

Self Cite

View full text Add to dashboard Cite

show abstract

“…While fully selfconsistent GW calculations (scGW ) are still scarce, non-self-consistent G 0 W 0 is by far the most commonly used variant, as it has been shown to lead to accurate IPs at a fraction of the cost of partially or fully self-consistent schemes. 9,18,23 However, while the G 0 W 0 correction can be readily applied to any DFT calcu-lation, a strong starting point dependence has been found, [8][9][10][11][12][13][15][16][17]20,[24][25][26][27][28][29][30] hence making the choice of the exchange-correlation functional in the underlying DFT calculation crucial for the accuracy of the calculated IPs and EAs.…”

Section: Introductionmentioning

confidence: 99%

Size-Dependence of Nonempirically Tuned DFT Starting Points for G₀W₀ Applied to π-Conjugated Molecular Chains

Bois

Körzdörfer

2017

J. Chem. Theory Comput.

View full text Add to dashboard Cite

GW calculations for predicting vertical ionization potentials (IPs) and electron affinities of molecules and clusters are known to show a significant dependence on the density functional theory (DFT) starting point. A number of nonempirical procedures to find an optimal starting point have been proposed, typically based on tuning the amount of HF exchange in the underlying hybrid functional specifically for the system at hand. For the case of π-conjugated molecular chains, these approaches lead to a significantly different amount of HF exchange for different oligomer sizes. In this study, we analyze if and how strongly this size dependence affects the ability of nonempirical tuning approaches to predict accurate IPs for π-conjugated molecular chains of increasing chain length. To this end, we employ three different nonempirical tuning procedures for the GW starting point to calculate the IP of polyene oligomers up to 22 repeat units and compare the results to highly accurate coupled-cluster calculations. We find that, despite its size dependence, using an IP-tuned hybrid functional as a starting point for GW yields excellent agreement with the reference data for all chain lengths.

show abstract

“…We shall resume this. Figure 3 (b) shows the errors with respect to experiments, reflecting the well-known starting-point dependence 1,2,11,12,17,[64][65][66][67][68] in a quantitative way. Although the improvement over LDA is already very impressive, G 0 W 0 @LDA still systematically underestimates band gaps, as already observed in the literature.…”

Section: A Band Gaps From (Generalized) Kohn-sham Calculationsmentioning

confidence: 95%

Probing the LDA-1/2 method as a starting point forG0W0calculations

et al. 2016

View full text Add to dashboard Cite

Employing the G0W0 approximation of Hedin's GW approach one can obtain quasi-particle energies of extended systems and molecules with good accuracy. However, for many materials, semi-local exchange-correlation functionals are unsatisfactory starting points for G0W0 calculations. Hybrid functionals often improve upon them, but at a substantially higher computational cost. As an alternative, we suggest the LDA-1/2 method, which provides reasonable band gaps, without being computationally involved. In this work, we systematically compare 3 starting points for G0W0: LDA, PBE0, and LDA-1/2. A selection of solids is chosen for this benchmark: C, Si, SiC, AlP, LiF, MgO, Ne, Ar, GaN, GaAs, CdS, ZnS, and ZnO. We demonstrate that LDA-1/2 is a good starting point in most cases, reducing the mean absolute error of band gaps by 50% when compared to the other 2 functionals.

show abstract

Length dependence of ionization potentials of transacetylenes: Internally consistent DFT/GWapproach

Cited by 33 publications

References 87 publications

Enforcing the linear behavior of the total energy with hybrid functionals: Implications for charge transfer, interaction energies, and the random-phase approximation

Enforcing the linear behavior of the total energy with hybrid functionals: Implications for charge transfer, interaction energies, and the random-phase approximation

Size-Dependence of Nonempirically Tuned DFT Starting Points for G₀W₀ Applied to π-Conjugated Molecular Chains

Probing the LDA-1/2 method as a starting point forG0W0calculations

Contact Info

Product

Resources

About

Length dependence of ionization potentials of transacetylenes: Internally consistent DFT/GWapproach

Cited by 33 publications

References 87 publications

Enforcing the linear behavior of the total energy with hybrid functionals: Implications for charge transfer, interaction energies, and the random-phase approximation

Enforcing the linear behavior of the total energy with hybrid functionals: Implications for charge transfer, interaction energies, and the random-phase approximation

Size-Dependence of Nonempirically Tuned DFT Starting Points for G0W0 Applied to π-Conjugated Molecular Chains

Probing the LDA-1/2 method as a starting point forG0W0calculations

Contact Info

Product

Resources

About

Size-Dependence of Nonempirically Tuned DFT Starting Points for G₀W₀ Applied to π-Conjugated Molecular Chains