Accurate molecular electrostatic potentials based on modified PRDDO/M wave functions: II. Electrostatic potentials inside the molecular van der Waals envelope

✍ Scribed by Marynick, Dennis S.

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 340 KB
• Volume: 18
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/(sici)1096-987x(199710)18:13<1682::aid-jcc10>3.0.co;2-k

✦ Synopsis

In part I of this series, the PESP parameterized electrostatic . potential method was described and applied to the calculation of electrostaticpotential-derived charges for a wide variety of organic and inorganic systems. Based on PRDDOrM wave functions and parameterized against ab initio MP2r6-31G UU 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 UU Ž . accuracy relative to MP2r6-31G of 0.03 A and 2.5 kcalrmol, respectively. Similarly, the location and well depths of minima in the regions of organic molecules are calculated to an accuracy of 0.08 A and 1.5 kcalrmol. PESP electrostatic potential maps are, in some cases, virtually indistinguishable from those obtained at the MP2r6-31G UU level.