Resolution of a challenge for solvation modeling: Calculation of dicarboxylic acid dissociation constants using mixed discrete-continuum solvation models

Aleksandr V. Marenich, Wendu Ding, Christopher J. Cramer, Donald G. Truhlar

Research output: Contribution to journalArticlepeer-review

66 Scopus citations

Abstract

First and second dissociation constants (pK a values) of oxalic acid, malonic acid, and adipic acid were computed by using a number of theoretical protocols based on density functional theory and using both continuum solvation models and mixed discrete-continuum solvation models. We show that fully implicit solvation models (in which the entire solvent is represented by a dielectric continuum) fail badly for dicarboxylic acids with mean unsigned errors (averaged over six pK a values) of 2.4-9.0 log units, depending on the particular implicit model used. The use of water-solute clusters and accounting for multiple conformations in solution significantly improve the performance of both generalized Born solvation models and models that solve the nonhomogeneous dielectric Poisson equation for bulk electrostatics. The four most successful models have mean unsigned errors of only 0.6-0.8 log units.

Original languageEnglish (US)
Pages (from-to)1437-1442
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume3
Issue number11
DOIs
StatePublished - Jun 7 2012

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