Free energies of hydration using restrained electrostatic potential derived charges via free energy perturbations and linear response Export

@article{henchman:99b, abstract = {To determine the reliability of the restrained electrostatic potential derived (REPD) charge method described in a companion article, the free energies of hydration of 22 simple organic molecules were calculated using free energy perturbations and linear response theory. Of the four charge sets examined using the free energy perturbation method, REPD/6-31+G* charges gave the closest agreement with the experiment, followed by conventional EPD charges derived at the 6-31G* level. The average absolute error for the former was 2.9 kJ mol-1 and for the latter was 3.5 kJ mol-1. The linear response method was then used to predict free energies of hydration based on the average van der Waals and electrostatic solute-solvent energies obtained from Monte Carlo computer simulations and solvent accessible surface areas. Use of the three parameter relationship gave a good agreement with the experiment. However, a number of simpler fitting functions were also examined and found to be only marginally less reliable. A careful statistical analysis of the linear response method is therefore needed.   {\copyright}1999 John Wiley \& Sons, Inc.   J Comput Chem 20: 499-510, 1999}, address = {Department of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, United Kingdom}, author = {Henchman, Richard H. and Essex, Jonathan W.}, citeulike-article-id = {3865930}, citeulike-linkout-0 = {http://dx.doi.org/10.1002/(SICI)1096-987X(19990415)20:5%3C499::AID-JCC3%3E3.0.CO;2-J}, citeulike-linkout-1 = {http://www3.interscience.wiley.com/cgi-bin/abstract/45001704/ABSTRACT}, doi = {10.1002/(SICI)1096-987X(19990415)20:5%3C499::AID-JCC3%3E3.0.CO;2-J}, journal = {Journal of Computational Chemistry}, keywords = {ab-initio, charges, free-energy, perturbation, quantum-mechanics, solvation}, number = {5}, pages = {499--510}, posted-at = {2009-01-08 23:33:59}, priority = {0}, title = {Free energies of hydration using restrained electrostatic potential derived charges via free energy perturbations and linear response}, url = {http://dx.doi.org/10.1002/(SICI)1096-987X(19990415)20:5%3C499::AID-JCC3%3E3.0.CO;2-J}, volume = {20}, year = {1999} }

TY - JOUR ID - henchman:99b L3 - citeulike-article-id:3865930 N2 - To determine the reliability of the restrained electrostatic potential derived (REPD) charge method described in a companion article, the free energies of hydration of 22 simple organic molecules were calculated using free energy perturbations and linear response theory. Of the four charge sets examined using the free energy perturbation method, REPD/6-31+G* charges gave the closest agreement with the experiment, followed by conventional EPD charges derived at the 6-31G* level. The average absolute error for the former was 2.9 kJ mol-1 and for the latter was 3.5 kJ mol-1. The linear response method was then used to predict free energies of hydration based on the average van der Waals and electrostatic solute-solvent energies obtained from Monte Carlo computer simulations and solvent accessible surface areas. Use of the three parameter relationship gave a good agreement with the experiment. However, a number of simpler fitting functions were also examined and found to be only marginally less reliable. A careful statistical analysis of the linear response method is therefore needed.   ©1999 John Wiley & Sons, Inc.   J Comput Chem 20: 499-510, 1999 IS - 5 JF - Journal of Computational Chemistry AD - Department of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, United Kingdom EP - 510 TI - Free energies of hydration using restrained electrostatic potential derived charges via free energy perturbations and linear response VL - 20 SP - 499 KW - ab-initio KW - charges KW - free-energy KW - perturbation KW - quantum-mechanics KW - solvation AU - Henchman, Richard AU - Essex, Jonathan PY - 1999/// UR - http://dx.doi.org/10.1002/(SICI)1096-987X(19990415)20:5%3C499::AID-JCC3%3E3.0.CO;2-J ER -