• DOI:10.1021/JA00105A030
• Corpus ID: 10518482

Accurate First Principles Calculation of Molecular Charge Distributions and Solvation Energies from Ab Initio Quantum Mechanics and Continuum Dielectric Theory

@article{Tannor1994AccurateFP,
  title={Accurate First Principles Calculation of Molecular Charge Distributions and Solvation Energies from Ab Initio Quantum Mechanics and Continuum Dielectric Theory},
  author={David J. Tannor and Bryan D. Marten and Robert B. Murphy and Richard A. Friesner and Doree Sitkoff and Anthony Nicholls and Barry Honig and Murco N. Ringnalda and William A. Goddard},
  journal={Journal of the American Chemical Society},
  year={1994},
  volume={116},
  pages={11875-11882}
}

• D. Tannor, B. Marten, +6 authors W. Goddard
• Published 1 December 1994
• Chemistry
• Journal of the American Chemical Society

In this paper, we combine high-level ab initio quantum chemical calculations with a continuum description of the solvent to obtain accurate solvation free energies of organic solutes in water. By using correlated wave functions at the generalized valence bondperfect pairing (GVB-PP) level, we are able to efficiently produce accurate gas-phase charge distributions. These are then used to obtain solvation energies in a self-consistent formalism which cycles through quantum chemical calculations in the solvent reaction field and continuum electrostatic calculations utilizing polarized solute charges. An average error of 0.6 kcal/mol for solvation energies is obtained for 29 molecules. A systematic discrepancy between theory and experiment is obtained for the difference in solvation free energy between several methylated and unmethylated primary amines and amides. This poses a major puzzle in theoretical modeling of solvation effects.