Premium
Evaluation of DFT Methods and Implicit Solvation Models for Anion‐Binding Host‐Guest Systems
Author(s) -
Young Lee Ga,
Bay Katherine L.,
Houk Kendall N.
Publication year - 2019
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201900032
Subject(s) - chemistry , solvation , density functional theory , polarizable continuum model , cryptand , supramolecular chemistry , implicit solvation , computational chemistry , aqueous solution , ion , affinities , halide , binding energy , hydrogen bond , crystallography , molecule , crystal structure , stereochemistry , inorganic chemistry , atomic physics , organic chemistry , physics
Although supramolecular chemistry is traditionally an experimental discipline, computations have emerged as important tools for the understanding of supramolecules. We have explored how well commonly used density functional theory quantum mechanics and polarizable continuum solvation models can calculate binding affinities of host‐guest systems. We report the calculation of binding affinities for eight host–guest complexes and compare our results to experimentally measured binding free energies that span the range from −2.3 to −6.1 kcal mol −1 . These systems consist of four hosts (biotin[6]uril, triphenoxymethane, cryptand, and bis‐thiourea) with different halide ions (F − , Cl − , Br − ) in various media including organic and aqueous. The mean average deviation (MAD) of calculated from measured Δ G a is 2.5 kcal mol −1 when using B3LYP‐D3 with either CPCM or PCM. This MAD value lowers even more by eliminating two outliers: 1.1 kcal mol −1 for CPCM and 1.2 kcal mol −1 for PCM. The best DFT and implicit solvation model combination that we have studied is B3LYP−D3 with either CPCM or PCM.