Prediction of Henry's law constant of benzene derivatives using quantum chemical continuum‐solvation models

摘要: Semiempirical (SM2, SM5.4A, MST-AM1, COSMO-AM1) and ab inito (HF/PCM-vdW, MP2//PCM-vdW, COSMO-DFT) dielectric continuum-solvation models as well the surface-tension model SM5.0R are analyzed with respect to predicting Henry's law constant at 25°C using a compound set of benzene 39 derivatives. Both hydrophilic hydrophobic compounds covered total variation in almost eight orders magnitude corresponding 44 kJ/mol, data is selected such that there cases where subtle changes molecular structure result substantial free energy solvation. The calculations SM2, COSMO-AM1, COSMO-DFT include solution-phase geometry optimization, initio results refer polarized basis sets double-zeta quality, two gradient-corrected functionals (BPW BLYP) being used for DFT-based models. show considerable differences performance between different models, among methods yielding solvation energies systematic error ranges from −0.9 kJ/mol (SM5.0R) 12.1 (MP2//PCM-vdW). In particular, nonelectrostatic contributions PCM-vdW do not correlate each other, omission component significantly improves relative trend. best statistics after scaling through linear regression achieved electrostatic MP2//PCM-vdW (r=0.94) (r=0.93). discussion includes detailed analyses pecularities associated certain functional groups, deviations expected relationship dipole moment energy, simple approach dispersion interaction cavitation by surface area terms differentiate individual atom types. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 17–34,