Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published May 18, 2022 | Submitted
Report Open

Visualization of Electron Density Changes Along Chemical Reaction Pathways

Abstract

We propose a simple procedure for visualizing the electron density changes (EDC) during a chemical reaction, which is based on a mapping of rectangular grid points for a stationary structure into (distorted) positions around atoms of another stationary structure. Specifically, during a small step along the minimum energy pathway (MEP), the displacement of each grid point is obtained as a linear combination of the motion of all atoms, with the contribution from each atom scaled by the corresponding Hirshfeld weight. For several reactions (identity S_N2, Claisen rearrangement, Diels-Alder reaction, [3+2] cycloaddition, and phenylethyl mercaptan attack on pericosine A), our EDC plots showed an expected reduction of electron densities around severed bonds (or those with the bond-order lowered), with the opposite observed for newly-formed or enhanced chemical bonds. The EDC plots were also shown for copper triflate catalyzed N₂O fragmentation, where the N–O bond weakening initially occurred on a singlet surface, but continued on a triplet surface after reaching the minimum-energy crossing point (MECP) between the two potential energy surfaces.

Additional Information

The content is available under CC BY 4.0 License. Chance Lander and Vardhan Satalkar contributed equally to this work. Financial support from the National Science Foundation (CHE-2102071 to ZY and YS; CHE-1566213 to KMN), the National Institutes of Health (R01GM135392 to YS), and the Cope Scholar Award (to KMN) are acknowledged. YS thanks Dr. Tom Cundari for suggesting [3+2] cycloaddition as a test case. YS also thanks Ginny Kim for helpful discussions. Computational resources and services used in this work were provided by the OU Supercomputing Center for Education and Research (OSCER).

Attached Files

Submitted - 10.26434_chemrxiv-2022-tfqnn.pdf

Files

10.26434_chemrxiv-2022-tfqnn.pdf
Files (7.4 MB)
Name Size Download all
md5:f02a870fff18b33b7220b31c62567df8
7.4 MB Preview Download

Additional details

Created:
August 22, 2023
Modified:
October 24, 2023