TY - JOUR
T1 - Surprisingly Good Performance of XYG3 Family Functionals Using a Scaled KS-MP3 Correlation
AU - Santra, Golokesh
AU - Semidalas, Emmanouil
AU - Martin, Jan M. L
N1 - Publisher Copyright: © 2021 The Authors. Published by American Chemical Society.
PY - 2021/9/30
Y1 - 2021/9/30
N2 - By adding a GLPT3 (third-order Görling-Levy perturbation theory, or KS-MP3) term E3 to the XYG7 form for a double hybrid, we are able to bring down WTMAD2 (weighted total mean absolute deviation) for the very large and chemically diverse GMTKN55 benchmark to an unprecedented 1.17 kcal/mol, competitive with much costlier composite wave function ab initio approaches. Intriguingly, (a) the introduction of E3 makes an empirical dispersion correction redundant; (b) generalized gradient approximation (GGA) or meta-GGA semilocal correlation functionals offer no advantage over the local density approximation (LDA) in this framework; (c) if a dispersion correction is retained, then simple Slater exchange leads to no significant loss in accuracy. It is possible to create a six-parameter functional with WTMAD2 = 1.42 that has no post-LDA density functional theory components and no dispersion correction in the final energy.
AB - By adding a GLPT3 (third-order Görling-Levy perturbation theory, or KS-MP3) term E3 to the XYG7 form for a double hybrid, we are able to bring down WTMAD2 (weighted total mean absolute deviation) for the very large and chemically diverse GMTKN55 benchmark to an unprecedented 1.17 kcal/mol, competitive with much costlier composite wave function ab initio approaches. Intriguingly, (a) the introduction of E3 makes an empirical dispersion correction redundant; (b) generalized gradient approximation (GGA) or meta-GGA semilocal correlation functionals offer no advantage over the local density approximation (LDA) in this framework; (c) if a dispersion correction is retained, then simple Slater exchange leads to no significant loss in accuracy. It is possible to create a six-parameter functional with WTMAD2 = 1.42 that has no post-LDA density functional theory components and no dispersion correction in the final energy.
UR - http://www.scopus.com/inward/record.url?scp=85116648599&partnerID=8YFLogxK
U2 - https://doi.org/10.1021/acs.jpclett.1c02838
DO - https://doi.org/10.1021/acs.jpclett.1c02838
M3 - مقالة
SN - 1948-7185
VL - 12
SP - 9368
EP - 9376
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 38
ER -