Robust All-Electron Optimization in Orbital-Free Density-Functional Theory Using the Trust-Region Image Method

Ryley, Matthew S.; Withnall, Michael; Irons, Tom J. P.; Helgaker, Trygve; Teale, Andrew M.

Abstract

We present a Gaussian-basis implementation of orbital-free density-functional theory (OF-DFT) in which the trust-region image method (TRIM) is used for optimization. This second-order optimization scheme has been constructed to provide benchmark all-electron results with very tight convergence of the particle-number constraint, associated chemical potential, and electron density. It is demonstrated that, by preserving the saddle-point nature of the optimization and simultaneously optimizing the density and chemical potential, an order of magnitude reduction in the number of iterations required for convergence is obtained. The approach is compared and contrasted with a new implementation of the nested optimization scheme put forward by Chan, Cohen, and Handy. Our implementation allows for semilocal kinetic-energy (and exchange-correlation) functionals to be handled self-consistently in all-electron calculations. The all-electron Gaussian-basis setting for these calculations will enable direct comparison with a wide range of standard high-accuracy quantum-chemical methods as well as with Kohn-Sham density-functional theory. We expect that the present implementation will provide a useful tool for analyzing the performance of approximate kinetic-energy functionals in finite systems.

Citation

Ryley, M. S., Withnall, M., Irons, T. J. P., Helgaker, T., & Teale, A. M. (2021). Robust All-Electron Optimization in Orbital-Free Density-Functional Theory Using the Trust-Region Image Method. Journal of Physical Chemistry A, 125(1), 459-475. https://doi.org/10.1021/acs.jpca.0c09502

• Journal Article Type: Article
• Acceptance Date: Dec 22, 2020
• Online Publication Date: Dec 24, 2020
• Publication Date: Jan 14, 2021
• Deposit Date: Jun 23, 2021
• Publicly Available Date: Dec 25, 2021
• Journal: Journal of Physical Chemistry A
• Print ISSN: 1089-5639
• Electronic ISSN: 1520-5215
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 125
• Issue: 1
• Pages: 459-475
• DOI: https://doi.org/10.1021/acs.jpca.0c09502
• Keywords: Physical and Theoretical Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/5173229
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.jpca.0c09502
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Journal of Physical Chemistry A, copyright© American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpca.0c09502