First-principles calculations of hybrid inorganic-organic interfaces: from state-of-the-art to best practice

• Published in: Physical chemistry chemical physics : PCCP Vol. 23; no. 14; pp. 8132 - 818
• Main Authors: Hofmann, Oliver T, Zojer, Egbert, Hörmann, Lukas, Jeindl, Andreas, Maurer, Reinhard J
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 14.04.2021; The Royal Society of Chemistry
• Subjects: Algorithms; Best practice; Chemistry; Density functional theory; Electronic properties; Electronic structure; First principles; Hybrid systems; Mathematical analysis; Self consistent fields
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/d0cp06605b

The computational characterization of inorganic-organic hybrid interfaces is arguably one of the technically most challenging applications of density functional theory. Due to the fundamentally different electronic properties of the inorganic and the organic components of a hybrid interface, the proper choice of the electronic structure method, of the algorithms to solve these methods, and of the parameters that enter these algorithms is highly non-trivial. In fact, computational choices that work well for one of the components often perform poorly for the other. As a consequence, default settings for one materials class are typically inadequate for the hybrid system, which makes calculations employing such settings inefficient and sometimes even prone to erroneous results. To address this issue, we discuss how to choose appropriate atomistic representations for the system under investigation, we highlight the role of the exchange-correlation functional and the van der Waals correction employed in the calculation and we provide tips and tricks how to efficiently converge the self-consistent field cycle and to obtain accurate geometries. We particularly focus on potentially unexpected pitfalls and the errors they incur. As a summary, we provide a list of best practice rules for interface simulations that should especially serve as a useful starting point for less experienced users and newcomers to the field. This work highlights the challenges and problems when modelling inorganic-organic interfaces and provides practical tips and suggestions for efficient calculations.