Aa. Rashin et al., INCORPORATION OF REACTION FIELD EFFECTS INTO DENSITY-FUNCTIONAL CALCULATIONS FOR MOLECULES OF ARBITRARY SHAPE IN SOLUTION, Biophysical chemistry, 51(2-3), 1994, pp. 375-392
An attempt is made to combine continuum reaction field approaches with
DFT ab initio calculations for quantitative evaluation of solvation e
ffects in chemical processes. The formalism of the combined method is
delineated along with its possibilities and limitations, and applied t
o several small model systems. It is found that DFT can provide dipole
moments in vacuum and in solution (e.g., for water) with accuracies (
0.1 D) that have not been reported with other methods. The results obt
ained suggest that agreement within similar to 1 kcal/mole can be expe
cted between calculated and experimental hydration enthalpies of polar
uncharged solutes. The results for ions are not as consistent as for
dipolar molecules, suggesting that accurate multipole representations
of the electron density of solutes may be required especially for ioni
c solutes.