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High‐level ab initio versus DFT calculations on (H 2 O 2 ) 2 and H 2 O 2 –H 2 O complexes as prototypes of multiple hydrogen bond systems
Author(s) -
González Leticia,
Mó Otilia,
Yáñez Manuel
Publication year - 1997
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/(sici)1096-987x(19970715)18:9<1124::aid-jcc2>3.0.co;2-t
Subject(s) - basis set , chemistry , ab initio , hydrogen bond , binding energy , computational chemistry , hydrogen peroxide , density functional theory , ab initio quantum chemistry methods , hydrogen , bond length , molecule , atomic physics , physics , organic chemistry
The performance of B‐LYP, B‐P86, B3‐LYP, B3‐P86, and B3‐PW91density functionals to describe multiple hydrogen bond systems was studied.For this purpose we have chosen the dimers of hydrogen peroxide and thehydrogen peroxide–water complexes. The geometries and vibrationalfrequencies obtained with a 6‐311+G(d,p) basis set were compared withthose obtained at the MP2 level using the same basis set expansion. Thecorresponding dimerization energies were obtained using a6‐311+G(3df,2p) basis set and compared with those obtained using theG2(MP2) theory. Red shiftings of the OH donor stretching frequencies werepredicted by all approaches investigated; however, in all cases, the DFTvalues were sizably larger than the MP2 ones. Similarly, the blue shiftingof the torsion of the hydrogen peroxide subunit was larger when evaluatedat the DFT level. All functionals reproduced the G2(MP2) relativestabilities of the different local minima quite well. With the exception ofthe B‐LYP and B3‐PW91 approaches, all functionals yielded binding energieswhich deviated from the G2(MP2) values by less than 0.5 kcal/mol, providedthat G2‐type basis sets were used and that the corresponding BSSEcorrections were included. © 1997 John Wiley & Sons, Inc. J Comput Chem 18: 1124–1135