Density functional theory (DFT) has become an invaluable tool across many domains in chemistry and materials science, a success made possible by the high accuracy and efficiency of modern density functional approximations (DFA). Despite the continued progress in functional design, conventional DFAs suffer from deficiencies caused by a poor description of the strong many-electron interaction (SMEI) arising from near-degeneracies and from a self-interaction error (SIE) due to the imperfect cancellation of the spurious classical Coulomb self-interaction [1,2]. Such deficiencies prevent accurate prediction of key properties important for energy applications, including band gaps, band alignments, stretched bonds, interactions with transition metal catalysts, charge transfer processes, and reaction barriers [3-6]. Despite enormous efforts to solve SIE and SMEI within DFT [3,7], there is not yet an efficient functional, applicable to both finite molecules and extended solids, that solves the SIE and SMEI deficiencies whilst maintaining standard DFT accuracy for systems around equilibrium [8]. We investigate the development of such a universal functional through a local hybrid construction that incorporates a space dependent local admixture of the exact-exchange energy density to build in the required non-local information. We have implemented a general local hybrid framework into the rapid development platform QUEST [9], capable of self-consistent calculations with local hybrid functionals. This code has been used to explore simple local mixing functions using kinetic energy densities, revealing important observations on the numerical stability of these ingredients. [1] A. J. Cohen, P. Mori-Sánchez, and W. Yang, Chemical Reviews 112, 289 (2011). [2] A. J. Cohen, P. Mori-Sánchez, and W. Yang, Science 321, 792 (2008). [3] J. P. Perdew, and A. Zunger, Physical Review B 23, 5048 (1981). [4] J. P. Perdew, R. G. Parr, M. Levy, and J. L. Balduz, Physical Review Letters 49, 1691 (1982). [5] J. P. Perdew, A. Ruzsinszky, G. I. Csonka, et. al. Physical Review A 76, 040501 (2007). [6] P. Mori-Sánchez, A. J. Cohen, and W. Yang, Physical review letters 100, 146401 (2008). [7] M. R. Pederson, A. Ruzsinszky, and J. P. Perdew, The Journal of chemical physics 140, 121103 (2014). [8] J. Sun, A. Ruzsinszky, and J. P. Perdew, Physical Review Letters 115, 036402 (2015). [9] QUantum Electronic Structure Techniques (QUEST) www.quest.codes

Utilizing advanced kinetic energy density based ingredients for novel local hybrid mixing functions

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.