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Performance of Range Separated Density Functional in Solvent Continuum: Tuning Long‐range Hartree–Fock Exchange for Improved Orbital Energies
Author(s) -
Boruah Abhijit,
Borpuzari Manash Protim,
Kar Rahul
Publication year - 2020
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26101
Subject(s) - hybrid functional , density functional theory , range (aeronautics) , orbital free density functional theory , consistency (knowledge bases) , eigenvalues and eigenvectors , dielectric , solvent , solvent effects , chemistry , computational chemistry , statistical physics , computational physics , materials science , molecular physics , quantum mechanics , physics , mathematics , geometry , organic chemistry , composite material
Performance of the density functionals mainly depends on the proper approximation of exchange‐correlation functionals. Modification of various parameters of such functionals, according to the demand of the system, has brought their accuracy level to a new height. Recent reports highlight that Long‐range Corrected (LC) functionals are not encouraging in reproducing orbital energies in solvent. Therefore, in this article, we have proposed a tuning scheme for the LC functional for improved orbital energies. In this scheme, the optimized long‐range HF exchange and the dielectric constant of the medium are included to modify the form of functionals. The proposed tuning is tested over a set of 103 molecules from IP131 database and fifteen solvent dielectrics. The tuned range separated functionals reproduce orbital eigenvalues in solvent continuum with good accuracy. More importantly, there is a consistency in the error for the tuned functional across the solvent media. © 2019 Wiley Periodicals, Inc.