Beyond Koopmans' theorem: electron binding energies in disordered materials

0517126 - ÚFCH JH 2020 RIV GB eng J - Journal Article
Muchová, E. - Slavíček, Petr
Beyond Koopmans' theorem: electron binding energies in disordered materials.
Journal of Physics-Condensed Matter. Roč. 31, č. 4 (2019), č. článku 043001. ISSN 0953-8984. E-ISSN 1361-648X
Institutional support: RVO:61388955
Keywords : density-functional-theory * separated hybrid functionals * valence ionization energies * charge-transfer states * kohn-sham orbitals * ab-initio dft * photoelectron-spectroscopy * excited-states * aqueous-solutions * greens-function * ionization
OECD category: Physical chemistry
Impact factor: 2.705, year: 2019
Method of publishing: Limited access

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.
Permanent Link: http://hdl.handle.net/11104/0302415