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Theoretical Prediction of the Hydrogen‐Bond Basicity p K HB
Author(s) -
Lamarche Olivier,
Platts James A.
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020118)8:2<457::aid-chem457>3.0.co;2-5
Subject(s) - hydrogen bond , gibbs free energy , chemistry , ab initio , bond energy , hydrogen fluoride , hydrogen , fluoride , computational chemistry , binding energy , thermodynamics , crystallography , molecule , inorganic chemistry , atomic physics , organic chemistry , physics
Ab initio and DFT calculations on around 65 hydrogen bond or Lewis bases and their complexes with hydrogen fluoride have been performed, and a range of calculated properties from both free bases and complexes correlated with p K HB , an experimental scale of hydrogen‐bond basicity. For the entire range of bases, we found that the hydrogen‐bond binding Gibbs free energy computed at the B3LYP/6‐31+G(d,p) level of theory linearly correlated with p K HB . Further improvements in the correlation and prediction of p K HB were possible with a non‐linear fit by considering the hydrogen bonding Gibbs free energy of another possible stereoisomeric 1:1 complex and/or that of a linear 2:1 complex, which included a second hydrogen fluoride.