New Methodology to Produce Sets of Valence Bond Structures with Enhanced Chemical Insights

Sourav Roy, Avital Shurki*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The valence bond (VB) theory uses localized orbitals, and its wave function is composed of a linear combination of various VB structures which are based on sets of spin functions. The VB structures are not unique, and different sets are used, Rumer sets being the most common for classical VB due to their advantage as being both easily obtained as linearly independent and meaningful. Yet, Rumer rules, which are responsible for the simplified process of obtaining the Rumer sets, are very restrictive. Furthermore, Rumer sets are best suited for cyclic systems; however, in noncyclic systems, structures resulting from Rumer rules are often not the most intuitive/suitable structures for these systems. We have developed a method to obtain chemically insightful structures, which is based on concepts of chemical bonding. The method provides sets of VB structures with improved chemical insight, which can also be controlled. Parallel to the Rumer structures, the chemical insight sets of structures are based on electron pair coupling, and hence, pictorially can be drawn similarly to the Lewis structures. Yet, different from Rumer rules, the chemical insight method, being more flexible, allows larger combinations of bonds as well as larger combinations of structures in the sets it offers, resulting in many more possible sets that are better adapted to the systems studied.

Original languageAmerican English
Pages (from-to) 3102–3111
Number of pages10
JournalJournal of Chemical Theory and Computation
Volume19
Issue number11
DOIs
StatePublished - May 2023

Bibliographical note

Funding Information:
We would like to thank Dr. Eran London for insightful discussion. We also acknowledge the Israel Science Foundation (grant no. 1691/17) and the Alex Grass Center for Drug Design and Synthesis of Novel Therapeutics for financial support.

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society

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