Donor and acceptor levels of organic photovoltaic compounds from first principles

Dabo, Ismaïla; Ferretti, Andrea; Park, Cheol-Hwan; Poilvert, Nicolas; Li, Yanli; Cococcioni, Matteo; Marzari, Nicola

doi:10.1039/c2cp43491a

Cited by 42 publications

(57 citation statements)

References 74 publications

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“…Other authors have suggested constraining the potentials of DFT calculations with the correct asymptotic forms [GL12], which is another approach ripe for energy-error analysis. Other alternatives include using Koopman's condition [DFPP13], or the use of a model for the exchange hole that avoids the delocalization effect on barrier heights [JCDD15]. The beauty of HF-DFT is that it bypasses the need to find a better potential or do a more expensive calculation.…”

Section: E Applications Of Energy-error Analysis and Other Approachesmentioning

confidence: 99%

The Importance of Being Inconsistent

Wasserman

Nafziger

Jiang

et al. 2017

Annu. Rev. Phys. Chem.

116

156

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We review the role of self-consistency in density functional theory. We apply a recent analysis to both Kohn-Sham and orbital-free DFT, as well as to Partition-DFT, which generalizes all aspects of standard DFT. In each case, the analysis distinguishes between errors in approximate functionals versus errors in the self-consistent density. This yields insights into the origins of many errors in DFT calculations, especially those often attributed to self-interaction or delocalization error. In many classes of problems, errors can be substantially reduced by using 'better' densities. We review the history of these approaches, many of their applications, and give simple pedagogical examples.

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Section: E Applications Of Energy-error Analysis and Other Approachesmentioning

confidence: 99%

The Importance of Being Inconsistent

Wasserman

Nafziger

Jiang

et al. 2017

Annu. Rev. Phys. Chem.

116

156

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“…Alternatively, one can step outside the KS scheme by introducing orbital-specific corrections, where different electrons of the KS system are subject to different potentials. This is achieved, e.g., using self-interaction correction methods [29,[99][100][101], DFT+U and Koopmans' compliant functionals [102][103][104][105][106][107][108][109][110][111], the LDA-1/2 method [112], Fritsche's generalized approach [113,114], or a scissors-like operator to the KS system that affects only the vacant states [115].…”

Section: Introductionmentioning

confidence: 99%

Fundamental gaps with approximate density functionals: The derivative discontinuity revealed from ensemble considerations

Kraisler

Kronik

2014

The Journal of Chemical Physics

101

102

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The fundamental gap is a central quantity in the electronic structure of matter. Unfortunately, the fundamental gap is not generally equal to the Kohn-Sham gap of density functional theory (DFT), even in principle. The two gaps differ precisely by the derivative discontinuity, namely, an abrupt change in slope of the exchange-correlation (xc) energy as a function of electron number, expected across an integer-electron point. Popular approximate functionals are thought to be devoid of a derivative discontinuity, strongly compromising their performance for prediction of spectroscopic properties. Here we show that, in fact, all exchange-correlation functionals possess a derivative discontinuity, which arises naturally from the application of ensemble considerations within DFT, without any empiricism. This derivative discontinuity can be expressed in closed form using only quantities obtained in the course of a standard DFT calculation of the neutral system. For small, finite systems, addition of this derivative discontinuity indeed results in a greatly improved prediction for the fundamental gap, even when based on the most simple approximate exchange-correlation density functional -the local density approximation (LDA). For solids, the same scheme is exact in principle, but when applied to LDA it results in a vanishing derivative discontinuity correction. This failure is shown to be directly related to the failure of LDA in predicting fundamental gaps from total energy differences in extended systems.

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“…In previous work 28,29,31,32,36 the calculation of α (v) was performed at fixed geometry, assuming the variation of the screening during the geometry optimization to be negligible. In this work we explore self-consistency for α (v) with respect to molecular geometry.…”

Section: Geometry and Screening Optimizationmentioning

confidence: 99%

“…As mentioned, KC functionals [26][27][28][29][30][31][32] can be seen as a generalization of DFT+U aimed at explicitly enforcing PWL to an entire electronic manifold. These functionals are obtained by removing, orbital-by-orbital, the nonlinear (Slater) contribution to the total energy and by replacing it by a linear (Koopmans) term.…”

Section: Piecewise Linearity and Self-interaction Errorsmentioning

confidence: 99%

“…Recently, Koopmans-compliant (KC) functionals were introduced [26][27][28][29][30][31][32] to enforce a generalized criterion of piecewise linearity (PWL) in the energy of approximate DFT functionals with respect to the fractional removal or addition of an electron from any orbital of the system. This PWL condition is a generalization to the entire manifold of the molecular DFT+U approach 33,34 , stemming from similar linearization ideas in the solid state.…”

Section: Introductionmentioning

confidence: 99%

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First-Principles Photoemission Spectroscopy of DNA and RNA Nucleobases from Koopmans-Compliant Functionals

Nguyen

Borghi

Ferretti

et al. 2016

J. Chem. Theory Comput.

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The need to interpret ultraviolet photoemission data strongly motivates the refinement of firstprinciples techniques able to accurately predict spectral properties. In this work we employ Koopmans-compliant functionals, constructed to enforce piecewise linearity in approximate density functionals, to calculate the structural and electronic properties of DNA and RNA nucleobases. Our results show that not only ionization potentials and electron affinities are accurately predicted with mean absolute errors < 0.1 eV, but also that calculated photoemission spectra are in excellent agreement with experimental ultraviolet photoemission spectra. In particular, the role and contribution of different tautomers to the photoemission spectra are highlighted and discussed in detail. The structural properties of nucleobases are also investigated, showing an improved description with respect to local and semilocal density-functional theory. Methodologically, our results further consolidate the role of Koopmans-compliant functionals in providing, through orbital-density-dependent potentials, accurate electronic and spectral properties.

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Donor and acceptor levels of organic photovoltaic compounds from first principles

Cited by 42 publications

References 74 publications

The Importance of Being Inconsistent

The Importance of Being Inconsistent

Fundamental gaps with approximate density functionals: The derivative discontinuity revealed from ensemble considerations

First-Principles Photoemission Spectroscopy of DNA and RNA Nucleobases from Koopmans-Compliant Functionals

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