Document Type

Article

Journal/Book Title

Journal of Computational Chemistry

Publication Date

10-30-2017

Publisher

John Wiley & Sons, Inc

Volume

39

Issue

9

First Page

500

Last Page

510

Abstract

The various heterodimers formed by a series of Lewis acids with NH3 as Lewis base are identified. Lewis acids include those that can form chalcogen (HSF and HSBr), pnicogen (H2PF and H2PBr), and tetrel (H3SiF and H3SiBr) bonds, as well as H‐bonds and halogen bonds. The molecular electrostatic potential (MEP) of each Lewis acid is considered in a number of ways. Pictorial versions show broad regions of positive and negative MEP, on surfaces that vary with respect to either the value of the chosen isopotential, or their distance from the nuclei. Specific points are identified where the MEP reaches a maximum on a particular isodensity surface (Vs,max). The locations and values of Vs,max were evaluated on different isodensity surfaces, and compared to the stabilities of the various equilibrium geometries. As the chosen isodensity is decreased, and the MEP maxima drift away from the molecule, some points maintain their angular positions with respect to the molecule, whereas others undergo a reorientation. The lowering isodensity also causes some of the maxima to disappear. In general, there is a fairly good correlation between the energetic ordering of the equilibrium structures and the values of Vs,max. A number of possible Lewis acid sites on the heteroaromatic imidazole ring were also considered and presents some cautions about application of Vs,max as the principal criterion for predicting equilibrium geometries. © 2017 Wiley Periodicals, Inc.

Comments

This is the peer reviewed version of the following article: Scheiner, S. I. (2018). Comparison of Various Means of Evaluating Molecular Electrostatic Potentials for Noncovalent Interactions. Journal of Computational Chemistry, 39(9), 500--510. http://dx.doi.org/10.1002/jcc.25085, which has been published in final form at https://doi.org/10.1002/jcc.25085. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

Included in

Chemistry Commons

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.