TY - JOUR

T1 - Piecewise linearity and spectroscopic properties from koopmans-compliant functionals

AU - Dabo, Ismaila

AU - Ferretti, Andrea

AU - Marzari, Nicola

N1 - Funding Information:
The authors are indebted to M. Cococcioni, N. Poilvert, G. Borghi, N. L. Nguyen, C.-H. Park, M. Marqués, E. K. U. Gross, S. de Gironcoli, and S. Baroni for valuable discussions and relevant suggestions. ID acknowledges partial support from the French National Research Agency through Grant ANR 12-BS04-0001 PANELS (Photovoltaics from Ab-initio Novel Electronic-structure Simulations). AF acknowledges partial support from Italian MIUR through Grant FIRB-RBFR08FOAL_001.
Publisher Copyright:
© Springer-Verlag Berlin Heidelberg 2014.

PY - 2014

Y1 - 2014

N2 - Density-functional theory is an extremely powerful and widely used tool for quantum simulations. It reformulates the electronic-structure problem into a functional minimization with respect to the charge density of interacting electrons in an external potential. While exact in principle, it is approximate in practice, and even in its exact form it is meant to reproduce correctly only the total energy and its derivatives, such as forces, phonons, or dielectric properties. Quasiparticle levels are outside the scope of the theory, with the exception of the highest occupied state, since this is given by the derivative of the energy with respect to the number of electrons. A fundamental property of the exact energy functional is that of piecewise linearity at fractional occupations in between integer fillings, but common approximations do not follow such piecewise behavior, leading to a discrepancy between total and partial electron removal energies. Since the former are typically well described, and the latter provide, via Janak’s theorem, orbital energies, this discrepancy leads to a poor comparison between predicted and measured spectroscopic properties. We illustrate here the powerful consequences that arise from.

AB - Density-functional theory is an extremely powerful and widely used tool for quantum simulations. It reformulates the electronic-structure problem into a functional minimization with respect to the charge density of interacting electrons in an external potential. While exact in principle, it is approximate in practice, and even in its exact form it is meant to reproduce correctly only the total energy and its derivatives, such as forces, phonons, or dielectric properties. Quasiparticle levels are outside the scope of the theory, with the exception of the highest occupied state, since this is given by the derivative of the energy with respect to the number of electrons. A fundamental property of the exact energy functional is that of piecewise linearity at fractional occupations in between integer fillings, but common approximations do not follow such piecewise behavior, leading to a discrepancy between total and partial electron removal energies. Since the former are typically well described, and the latter provide, via Janak’s theorem, orbital energies, this discrepancy leads to a poor comparison between predicted and measured spectroscopic properties. We illustrate here the powerful consequences that arise from.

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U2 - 10.1007/128_2013_504

DO - 10.1007/128_2013_504

M3 - Article

AN - SCOPUS:84921730266

SN - 0340-1022

VL - 347

SP - 193

EP - 234

JO - Topics in Current Chemistry

JF - Topics in Current Chemistry

ER -