Premium
Accurate molecular electrostatic potentials based on modified PRDDO/M wave functions: II. Electrostatic potentials inside the molecular van der Waals envelope
Author(s) -
Marynick Dennis S.
Publication year - 1997
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(199710)18:13<1682::aid-jcc10>3.0.co;2-k
Subject(s) - ab initio , chemistry , van der waals force , maxima and minima , computational chemistry , ab initio quantum chemistry methods , molecule , wave function , electrostatics , molecular physics , chemical physics , atomic physics , physics , mathematics , organic chemistry , mathematical analysis
In part I of this series, the PESP (parameterized electrostatic potential) method was described and applied to the calculation of electrostatic‐potential‐derived charges for a wide variety of organic and inorganic systems. Based on PRDDO/M wave functions and parameterized against ab initio MP2/6‐31G** calculations, PESP is an order of magnitude faster than ab initio STO‐3G calculations, while achieving a level of accuracy that rivals that of far more sophisticated ab initio methods. In this study, the application of the PESP method to the high potential regions of molecules containing H, C, N, O, F, P, S, Cl, and Br is described. For a collection of 48 molecules and 55 distinct lone pair minima, PESP yields the location and depth of lone pair minima to an average accuracy (relative to MP2/6‐31G**) of 0.03 Å and 2.5 kcal/mol, respectively. Similarly, the location and well depths of minima in the π regions of organic molecules are calculated to an accuracy of 0.08 Å and 1.5 kcal/mol. PESP electrostatic potential maps are, in some cases, virtually indistinguishable from those obtained at the MP2/6‐31G** level. © 1997 John Wiley & Sons, Inc. J Comput Chem 18 : 1682–1693, 1997