Density functional study of hydrogen-bonded systems: from gas-phase adducts to catalytically relevant systems

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

“…This topic has been largely investigated in the last two decades, the water dimer being probably the most intensively studied hydrogen bonded system . Among the standard density functionals frequently used in periodic calculations, B3LYP and BLYP have been shown to slightly underestimate the binding energy and the R O–O distance, while both slightly overestimate the O–H stretching frequency shift in an H-donor OH, compared with MP2 and experimental data. − The PBE functional, while providing accurate interaction energies, underestimates the R O–O distance somewhat more and predicts larger frequency shifts, and its reliability is closely connected to the bond directionality . For the most specific case of hydroxyl groups in ionic crystals like β-Be(OH) 2 and Mg(OH) 2 it was proven that B3LYP OH frequency shifts are in better agreement with experiment than those resulting from PW91 functional, which were definitely overestimated.…”