MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions. Issue 8 (4th May 2016)

• Record Type: Journal Article
• Authors: Yu, Haoyu S.; He, Xiao; Li, Shaohong L.; Truhlar, Donald G.
• Is Part Of: Chemical science. Volume 7:Issue 8(2016:Aug.)
• Page Start: 5032
• Page End: 5051
• Publication Date: 2016-05-04
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c6sc00705h
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : We report a global-hybrid approximation, MN15, to the exchange–correlation functional of Kohn–Sham theory with broadly accurate performance for both multi-reference and single-reference systems. Abstract : Kohn–Sham density functionals are widely used; however, no currently available exchange–correlation functional can predict all chemical properties with chemical accuracy. Here we report a new functional, called MN15, that has broader accuracy than any previously available one. The properties considered in the parameterization include bond energies, atomization energies, ionization potentials, electron affinities, proton affinities, reaction barrier heights, noncovalent interactions, hydrocarbon thermochemistry, isomerization energies, electronic excitation energies, absolute atomic energies, and molecular structures. When compared with 82 other density functionals that have been defined in the literature, MN15 gives the second smallest mean unsigned error (MUE) for 54 data on inherently multiconfigurational systems, the smallest MUE for 313 single-reference chemical data, and the smallest MUE on 87 noncovalent data, with MUEs for these three categories of 4.75, 1.85, and 0.25 kcal mol −1, respectively, as compared to the average MUEs of the other 82 functionals of 14.0, 4.63, and 1.98 kcal mol −1 . The MUE for 17 absolute atomic energies is 7.4 kcal mol −1 as compared to an average MUE of the other 82 functionals of 34.6 kcal mol −1 . We further tested MN15 for 10 transition-metal coordination energies, the entire S66x8 database of noncovalent interactions, 21 transition-metal reaction barrier heights, 69 electronic excitation energies of organic molecules, 31 semiconductor band gaps, seven transition-metal dimer bond lengths, and 193 bond lengths of 47 organic molecules. The MN15 functional not only performs very well for our training set, which has 481 pieces of data, but also performs very well for our test set, which has 823 data that are not in our training set. The test set includes both ground-state properties and molecular excitation energies. For the latter MN15 achieves simultaneous accuracy for both valence and Rydberg electronic excitations when used with linear-response time-dependent density functional theory, with an MUE of less than 0.3 eV for both types of excitations.