Beyond Koopmans' theorem: electron binding energies in disordered materials. (17th December 2018)

• Record Type: Journal Article
• Authors: Muchová, Eva; Slavíček, Petr
• Is Part Of: Journal of physics. Volume 31:Number 4(2019)
• Publication Date: 2018-12-17
• Subjects: ionization -- Koopmans' theorem -- one electron energies -- IP theorem; Condensed matter -- Periodicals; Matière condensée -- Périodiques; Vaste stoffen; Vloeistoffen; Natuurkunde; Electronic journals; Computer network resources; 530.4105
• DOI: 10.1088/1361-648X/aaf130
• Languages: English
• ISSNs: 0953-8984

Abstract

Abstract: The topical review focuses on calculating ionization energies (IE), or electronic polarons in quasi-particle terminology, in large disordered systems, e.g. for a solute dissolved in a molecular solvent. The simplest estimate of the ionization energy is provided by one-electron energies in the Hartree–Fock theory, but the calculated quantities are not accurate. Density functional theory as many-body theory provides a principal opportunity for calculating one-electron energies including correlation and relaxation effects, i.e. the true energies of electronic polarons. We argue that such a principal possibility materializes within the concept of optimally tuned range-separated hybrid functionals (OT-RSH). We describe various schemes for optimal tuning. Importantly, the OT-RSH scheme is investigated for systems capped with dielectric continuum, providing a consistent picture on the QM/dielectric boundary. Finally, some limitations and open issues of the OT-RSH approach are addressed.