Using dispersion-corrected density functional theory to understand supramolecular binding thermodynamics

摘要: A recently published theoretical approach employing a nondynamic structure model using dispersion-corrected density functional theory (DFT-D3) to calculate equilibrium free energies of association (Chem. Eur. J., 2012, 18, 9955–9964) is illustrated by its application eight new supramolecular complexes. We compare with experimentally known binding constants which span the range from −3.3 −20.3 kcal mol−1. The mean deviation calculated measured ΔGa results in 0.4 mol−1, absolute 1.8 mol−1 excluding two outliers for computed solvation are identified as largest error source. survey previous applications and related computational studies given underlining good accuracy. It concluded that structures gas phase interaction can be routinely high accuracy (relative errors 5–10%) complexes about 200–300 atoms.