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Performance assessment of density‐functional methods for study of charge‐transfer complexes
Author(s) -
Liao MengSheng,
Lu Yun,
Scheiner Steve
Publication year - 2003
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.10226
Subject(s) - intermolecular force , density functional theory , excitation , hybrid functional , charge exchange , charge (physics) , chemistry , transfer (computing) , computational chemistry , thermodynamics , atomic physics , chemical physics , molecular physics , molecule , physics , quantum mechanics , ion , computer science , organic chemistry , parallel computing
Various density functionals are applied to a number of weakly bound intermolecular π–π charge‐transfer (CT) complexes. Most functionals, including the recently developed m PWPW91 and m PW1PW91, grossly underestimate experimental excitation energies; good agreement is obtained only with the half‐and‐half hybrid BH&HLYP functional. PW91PW91 provides the best agreement with intermolecular distances measured in crystal, while the BH&HLYP values are about 0.1 Å too long. Various hybrid functionals with nonlocal exchange correction provide binding energies that compare favorably with the experimental heats of formation measured in solution. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 623–631, 2003
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