Exchange-Correlation Functionals with Broad Accuracy, Including Single- and MultiReference Molecules and Lattice Constants Haoyu S. Yu,a Xiao He,b Wenjing Zhang,c Sijie Luo,a Pragya Verma,a and Donald G. Truhlara a. Department of Chemistry, University of Minnesota b. Institute of Theoretical and Computational Science, East China Normal University c. College of Chemistry and Molecular Engineering, Zhengzhou University The accuracy of Kohn-Sham density functional theory depends on the exchange-correlation (xc) functional. Functionals of the generalized gradient approximation (GGA) form have been popular because of their low cost, locality, and simplicity, but no GGA is able to predict good results for all kinds of systems of interest including energies of single-reference and multireference molecules and lattice constants of solids. Nonseparable gradient approximations (NGAs) can achieve better accuracy on a broad test set of molecular and solid-state data, as demonstrated by the N12 functional [1]. We are currently designing a new NGA, called N14, which is parameterized with a broader data set than N12 and with smoothness constraints. We are also designing a new meta-NGA, called MN14-L, which is parameterized with the same database as N14 and with a new function α of the kinetic energy density [2] and smoothness constraints. Here we present β versions of N14 and MN14-L and show that the former has better accuracy for a broad chemistry database than any previous density functional depending only on spin densities and their gradients (i.e., GGAs or NGAs), and it also has good accuracy for lattice constants. The latter has better accuracy than any previous functional. Table 1. Mean unsigned error (MUE in kcal/mol) for chemical energy (CE390) database. Functional Type MUE MN14-‐Lβ M06 MN12-‐SX MN12-‐L M06-‐L M11 N14β M11-‐L O3LYP OreLYP B3LYP OLYP SOGGA11 TPSS N12 BLYP PBE GVWN5 local nonlocal nonlocal local local nonlocal local local nonlocal local nonlocal local local local local local local local meta-‐NGA global-‐hybrid meta-‐GGA screened-‐exchange meta-‐NGA meta-‐NGA meta-‐GGA range-‐separated hybrid meta-‐GGA NGA meta-‐GGA with local range separation global-‐hybrid GGA GGA global-‐hybrid GGA GGA GGA meta-‐GGA NGA GGA GGA LSDA 2.24 3.00 3.58 3.74 3.86 3.87 4.33 4.38 4.42 4.78 5.04 5.25 5.53 5.66 5.86 6.13 7.89 32.83 [1] R. Peverati, D. G. Truhlar, J. Chem. Theory Comput. 8 (2012) 2310. [2] J. Sun, B. Xiao, Y. Fang, R. Haunschild, P. Hao, A. Ruzsinsky, G. I. Csonka, G. E. Scuseria, J. P. Perdew. Phys. Rev. Lett. 111 (2013) 106401
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