ONIOM meets xtb: efficient, accurate, and robust multi-layer simulations across the periodic table

The computational treatment of large molecular structures is of increasing interest in fields of modern chemistry. Accordingly, efficient quantum chemical approaches are needed to perform sophisticated investigations on such systems. This engaged the development of the well-established Our own N-layered integrated molecular orbital and molecular mechanics (ONIOM) multi-layer scheme [L. W. Chung et al., Chem. Rev., 2015, 115, 5678-5796]. In this work, we present the specific implementation of the ONIOM scheme into the xtb semi-empirical extended tight-binding program package and its application to challenging transition-metal complexes. The efficient and broadly applicable GFNn-xTB and -FF methods are applied in the ONIOM framework to elucidate reaction energies, geometry optimizations, and explicit solvation effects for metal-organic systems with up to several hundreds of atoms. It is shown that an ONIOM-based combination of density functional theory, semi-empirical, and force-field methods can be used to drastically reduce the computational costs and thus enable the investigation of huge systems at almost no significant loss in accuracy.

Automated summary

Efficient quantum chemical methods are required for the computational treatment of large molecular structures. The ONIOM multi-layer scheme has been successfully implemented into the xtb program package and applied to transition-metal complexes with hundreds of atoms. By combining density functional theory, semi-empirical, and force-field methods in the ONIOM framework, computational costs can be significantly reduced without sacrificing accuracy.