Next-generation non-local van der Waals density functional

TL;DR

The paper introduces vdW-DF3, a new non-local density functional that improves accuracy for van der Waals interactions, especially at larger separations, by incorporating a semi-empirical approach based on insights from two decades of development.

Contribution

vdW-DF3 is the first major update to the original vdW-DF functional, introducing a new functional form and semi-empirical parameters to enhance performance across diverse systems.

Findings

vdW-DF3 outperforms previous functionals at larger separations

Benchmark results show good overall accuracy of vdW-DF3

Semi-empirical parameters improve functional flexibility

Abstract

The fundamental ideas for a non-local density functional theory -- capable of reliably capturing van der Waals interaction -- were already conceived in the 1990's. In 2004, a seminal paper introduced the first practical non-local exchange-correlation functional called vdW-DF, which has become widely successful and laid the foundation for much further research. However, since then, the functional form of vdW-DF has remained unchanged. Several successful modifications paired the original functional with different (local) exchange functionals to improve performance and the successor vdW-DF2 also updated one internal parameter. Bringing together different insights from almost two decades of development and testing, we present the next-generation non-local correlation functional called vdW-DF3, in which we change the functional form while staying true to the original design philosophy. Although many popular functionals show good performance around the binding separation of van der Waals complexes, they often result in significant errors at larger separations. With vdW-DF3, we address this problem by taking advantage of a recently uncovered and largely unconstrained degree of freedom within the vdW-DF framework that can be constrained through empirical input, making our functional semi-empirical. For two different parameterizations, we benchmark vdW-DF3 against a large set of well-studied test cases and compare our results with the most popular functionals, finding good performance in general for a wide array of systems and a significant improvement in accuracy at larger separations. Finally, we discuss the achievable performance within the current vdW-DF framework, the flexibility in functional design offered by vdW-DF3, as well as possible future directions for non-local van der Waals density functional theory.