Accelerating Kohn–Sham response theory using density fitting and the auxiliary-density-matrix method

Kumar, Chandan; Fliegl, Heike; Jensen, Frank; Teale, Andrew M.; Reine, Simen; Kjaergaard, Thomas

Abstract

An extension of the formulation of the atomic‐orbital‐based response theory of Larsen et al., JCP 113, 8909 (2000) is presented. This new framework has been implemented in LSDalton and allows for the use of Kohn‐Sham density‐functional theory with approximate treatment of the Coulomb and Exchange contributions to the response equations via the popular resolution‐of‐the‐identity approximation as well as the auxiliary‐density matrix method (ADMM). We present benchmark calculations of ground‐state energies as well as the linear and quadratic response properties: vertical excitation energies, polarizabilities, and hyperpolarizabilities. The quality of these approximations in a range of basis sets is assessed against reference calculations in a large aug‐pcseg‐4 basis. Our results confirm that density fitting of the Coulomb contribution can be used without hesitation for all the studied properties. The ADMM treatment of exchange is shown to yield high accuracy for ground‐state and excitation energies, whereas for polarizabilities and hyperpolarizabilities the performance gain comes at a cost of accuracy. Excitation energies of a tetrameric model consisting of units of the P700 special pigment of photosystem I have been studied to demonstrate the applicability of the code for a large system.

Citation

Kumar, C., Fliegl, H., Jensen, F., Teale, A. M., Reine, S., & Kjaergaard, T. (in press). Accelerating Kohn–Sham response theory using density fitting and the auxiliary-density-matrix method. International Journal of Quantum Chemistry, https://doi.org/10.1002/qua.25639

• Journal Article Type: Article
• Acceptance Date: Mar 27, 2018
• Online Publication Date: May 9, 2018
• Deposit Date: May 10, 2018
• Publicly Available Date: May 10, 2019
• Journal: International Journal of Quantum Chemistry
• Print ISSN: 0020-7608
• Electronic ISSN: 1097-461X
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• DOI: https://doi.org/10.1002/qua.25639
• Keywords: Kohn-Sham DFT response theory, Density fitting, RI, ADMM
• Public URL: https://nottingham-repository.worktribe.com/output/931815
• Publisher URL: https://onlinelibrary.wiley.com/doi/full/10.1002/qua.25639
• Additional Information: This is the peer reviewed version of the following article: Kumar, Chandan and Fliegl, Heike and Jensen, Frank and Teale, Andrew M. and Reine, Simen and Kjaergaard, Thomas (2018) Accelerating Kohn–Sham response theory using density fitting and the auxiliary-density-matrix method. International Journal of Quantum Chemistry . ISSN 0020-7608 , which has been published in final form at https://onlinelibrary.wiley.com/doi/full/10.1002/qua.25639. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
• Contract Date: May 10, 2018