Abstract
The optimum size of the cavity accommodating a solute in the reaction field theory of solvation is considered by empirical calibration of the results of electronic structure calculations against experiment. To isolate the long range electrostatic free energy contributions treated by reaction field theory from the many other short range contributions not explicitly considered, computational results are compared to experimental determinations of conformational free energy differences in polar solutes having two or more stable or metastable isomers. When the cavity shape is defined by a solute electronic isodensity contour, it is found that the best overall agreement with experiment is obtained with a cavity size corresponding to the 0.001 a.u. contour.
| Original language | English |
|---|---|
| Pages (from-to) | 10543-10558 |
| Number of pages | 16 |
| Journal | Journal of Chemical Physics |
| Volume | 109 |
| Issue number | 24 |
| DOIs | |
| State | Published - 1998 |
Bibliographical note
Funding Information:The authors gratefully acknowledge the supports from the Ministry of Industry and Information Technology of China (Grant No. [2013]418), the National High Technology Research and Development Program of China (863 Program, Grant No. 2013AA09A216), the National Nature Science Foundation of China (Grant No. 51504149), the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (Grant No. 51521004), the Postdoctoral Science Foundation of China (Grant No. 2015M570366) and the Program of Shanghai Academic Research Leader (Grant No. 16XD1401500).
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry