Premium
Can B3LYP be improved by optimization of the proportions of exchange and correlation functionals?
Author(s) -
Lu Lilin
Publication year - 2015
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24876
Subject(s) - hybrid functional , correlation , density functional theory , component (thermodynamics) , work (physics) , statistical physics , molecule , optimization algorithm , mathematics , computational chemistry , chemistry , materials science , physics , thermodynamics , mathematical optimization , quantum mechanics , geometry
B3LYP is the most famous hybrid density functional theory model, which includes Hartree–Fock exchange, local exchange, gradient exchange correction, local correlation, and gradient correlation correction. Historically, the relative weight of each component in B3LYP, which is controlled by three empirical parameters ( a 0 , a x , a c ), has not been optimized. In this work, we perform global optimization against accurate experimental reference, optimal empirical parameters, and the better version of B3LYP are obtained and denoted as OpB3LYP. The performance of OpB3LYP is widely tested over many species and chemical properties, the results show that the computational accuracy is significantly improved as compared to original B3LYP and the serious size dependence of B3LYP is remarkably overcome by the employment of OpB3LYP. The comparative assessment of OpB3LYP and other prevalent functionals indicates that OpB3LYP is a promising functional for large molecules. © 2015 Wiley Periodicals, Inc.