Density functional approximations for orbital energies and total energies of molecules and solids

Evert Jan Baerends*

*Corresponding author for this work

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Abstract

The relation of Kohn-Sham (KS) orbital energies to ionization energies and electron affinities is different in molecules and solids. In molecules, the local density approximation (LDA) and generalized gradient approximations (GGA) approximate the exact ionization energy (I) and affinity (A) rather well with self-consistently calculated (total energy based) ILDFA and ALDFA, respectively. The highest occupied molecular orbital (HOMO) energy and lowest unoccupied molecular orbital (LUMO) energy, however, differ significantly (by typically 4-6 eV) from these quantities, ϵHLDFA(mol)>-I(mol)≈-ILDFA(mol), ϵLLDFA(mol)<-A(mol)≈-ALDFA(mol). In solids, these relations are very different, due to two effects. The (almost) infinite extent of a solid makes the difference of orbital energies and (L)DFA calculated ionization energy and affinity disappear: in the solid state limit, ϵH(L)DFA(solid)=-I(L)DFA(solid) and ϵL(L)DFA(solid)=-A(L)DFA(solid). Slater's relation ∂E/∂ni = ϵi for local density functional approximations (LDFAs) [and Hartree-Fock (HF) and hybrids] is useful to prove these relations. The equality of LDFA orbital energies and LDFA calculated -ILDFA and -ALDFA in solids does not mean that they are good approximations to the exact quantities. The LDFA total energies of the ions with a delocalized charge are too low, hence ILDFA(solid) < I and ALDFA(solid) > A, due to the local-approximation error, also denoted delocalization error, of LDFAs in extended systems. These errors combine to make the LDFA orbital energy band gap considerably smaller than the exact fundamental gap, ϵLLDFA(solid)-ϵHLDFA(solid)=ILDFA(solid)-ALDFA(solid)<I-A (the LDFA band gap problem). These results for density functional approximations are compared to exact KS and to HF and hybrids. For the exact KS HOMO energy, one has ϵHKS=-I. The exact KS LUMO energy does not approximate the experimental -A (neither in molecules nor in solids), but is considerably below, which is the main reason for the exact KS HOMO-LUMO energy gap being considerably below the fundamental gap I - A (the exact KS band gap problem).

Original languageEnglish
Article number054105
Pages (from-to)1-17
Number of pages17
JournalJournal of Chemical Physics
Volume149
Issue number5
Early online date7 Aug 2018
DOIs
Publication statusPublished - 7 Aug 2018

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