Theoretical prediction of linear free energy relationships using proton nucleomers |
| |
| Authors: | Giovanni La Macchia Laura Gagliardi Geoffrey S Carlson Ashley N Jay Erik Davis Christopher J Cramer |
| |
| Institution: | 1. Department of Physical Chemistry, Sciences II University of Geneva, 30 Quai Ernest Ansermet, CH‐1211 Geneva 4, Switzerland;2. Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455‐0431, USA |
| |
| Abstract: | Values of σ and σ+, for use in linear free energy relationships, are determined for para hydrogen atoms having nuclear charges other than 1 (nucleomers). Hammett ρ values for a variety of free energies of activation, reaction, and other extrathermodynamic properties (e.g., vibrational frequencies) are computed therefrom and compared to those computed using typical para functional groups. The nucleomer correlations show excellent qualitative agreement with standard correlations but the quantitative agreement is less good, typically underestimating the standard ρ‐value by 10–60%. Copyright © 2007 John Wiley & Sons, Ltd. |
| |
| Keywords: | Hammett plot computational chemistry substitution effects linear free energy relationship |
|
|
