High-level Ab initio versus DFT calculations on (H2O2)2 and H2O2-H2O complexes as prototypes of multiple hydrogen bond systems

Abstract

The performance of B-LYP, B-P86, B3-LYP, B3-P86, and B3-PW91 density functionals to describe multiple hydrogen bond systems was studied. For this purpose we have chosen the dimers of hydrogen peroxide and the hydrogen peroxide-water complexes. The geometries and vibrational frequencies obtained with a 6-311 + G(d, p) basis set were compared with those obtained at the MP2 level using the same basis set expansion. The corresponding dimerization energies were obtained using a 6-311 + G(3df, 2p) basis set and compared with those obtained using the G2(MP2) theory. Red shiftings of the OH donor stretching frequencies were predicted by all approaches investigated; however, in all cases, the DFT values were sizably larger than the MP2 ones. Similarly, the blue shifting of the torsion of the hydrogen peroxide subunit was larger when evaluated at the DFT level. All functionals reproduced the G2(MP2) relative stabilities of the different local minima quite well. With the exception of the B-LYP and B3-PW91 approaches, all functionals yielded binding energies which deviated from the G2(MP2) values by less than 0.5 kcal/mol, provided that G2-type basis sets were used and that the corresponding BSSE corrections were included. © 1997 by John Wiley & Sons, Inc.