CAN CONTEMPORARY DENSITY-FUNCTIONAL THEORY YIELD ACCURATE THERMODYNAMICS FOR HYDROGEN-BONDING

Thermodynamic characteristics of dimerization were calculated for six molecules (including water, alcohols, and carboxylic acids) using density functional theory (DFT) methods and compared to corresponding experimental data. Basis set superposition error for different basis sets including polarization and diffuse Gaussian functions was calculated using the full counterpoise procedure. Ten out of twelve thermodynamic dimerization characteristics calculated with DZVPD/TZVPD basis sets agree with one of the available experimental values with near chemical accuracy (approximate to 1 kcal/mol). It is concluded that DFT/DZVPD/TZVPD calculations can yield not only accurate molecular dipole moments, but also rather accurate thermodynamics of hydrogen bonding.