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 dens ity functional theory (DFT) methods and compared to corresponding expe rimental data. Basis set superposition error for different basis sets including polarization and diffuse Gaussian functions was calculated u sing the full counterpoise procedure. Ten out of twelve thermodynamic dimerization characteristics calculated with DZVPD/TZVPD basis sets ag ree with one of the available experimental values with near chemical a ccuracy (approximate to 1 kcal/mol). It is concluded that DFT/DZVPD/TZ VPD calculations can yield not only accurate molecular dipole moments, but also rather accurate thermodynamics of hydrogen bonding.