Charge Density Analysis Attending Bond Torsion: A Bond Bundle Case Study

Authors: Jordan Goss, Tim Wilson, Amanda Morgenstern, Mark Eberhart

For nearly a century chemical understanding has been tied to the properties of bonds, though more often than not, these bond properties are rooted in molecular orbital or valence bond representations of the electronic structure. Technological advances, however, are allowing for experimental measurements of the density via high resolution x-ray diffraction, while theoretical insights are opening the door to its direct calculation using fast and potentially versatile orbital free DFT methods. Capitalizing on these emerging tools without sacrificing hard won orbital derived understanding has spurred a search for density based representations that deliver the same information available from the orbital perspective. We show that recent extensions of the QTAIM formalism are useful as a means of recovering some of the bond properties that have become an intrinsic part of our chemical understanding. Specifically, we compute from the density the changing bond order accompanying the rotation about a double bond using the well-studied fulvene molecule as a test case. We compare the picture that emerges from this density based perspective with that stemming from molecular orbital approaches and argue that the two viewpoints are compatible.

Comments: 19 Pages.

Download: PDF

Submission history

[v1] 2018-03-19 12:55:35

Unique-IP document downloads: 225 times is a pre-print repository rather than a journal. Articles hosted may not yet have been verified by peer-review and should be treated as preliminary. In particular, anything that appears to include financial or legal advice or proposed medical treatments should be treated with due caution. will not be responsible for any consequences of actions that result from any form of use of any documents on this website.

Add your own feedback and questions here:
You are equally welcome to be positive or negative about any paper but please be polite. If you are being critical you must mention at least one specific error, otherwise your comment will be deleted as unhelpful.

comments powered by Disqus