The fundamental ideas for a non-local density functional theory—capable of reliably capturing van der Waals interactions—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.
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Assessment of the Performance of Optimally Tuned Range‐Separated Hybrid Functionals for Nuclear Magnetic Shielding Calculations
The performance of optimally tuned range‐separated hybrid (OT‐RSH) functional calculations in predicting accurate isotropic nuclear magnetic shielding (σ) and chemical shift values is examined. To that end, the results of OT‐RSH and other approximate density functional theory calculations are assessed against recently published benchmark CCSD(T) calculations for a test set consisting of several molecules and bond types. It is found that for atoms in single bonds with a large paramagnetic contribution to σ, OT‐RSH offers a significant improvement in prediction of shielding constants over popular semi‐local and hybrid density functionals, yielding non‐empirical results that are as accurate as those of semi‐empirical density functionals often used for prediction of shielding constants. This success is attributed to the improved fundamental gap prediction of the OT‐RSH approach. For atoms in multiple bonds, however, larger errors often persist. By comparing OT‐RSH and recently reported double‐hybrid functional results, the remaining difficulties are traced to significant non‐local correlation.
more » « less- Award ID(s):
- 1855470
- NSF-PAR ID:
- 10169947
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Theory and Simulations
- Volume:
- 3
- Issue:
- 8
- ISSN:
- 2513-0390
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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