An official website of the United States government
Here’s how you know
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
Secure .gov websites use HTTPS
A lock (
) or https:// means you’ve safely connected to the .gov website. Share sensitive information only on official, secure websites.
Predicting Unexpected Chemical Reactions by Isopotential Searching
Published
Author(s)
Karl K. Irikura, Russell D. Johnson III
Abstract
The reactions of a chemical system are dictated by the corresponding potential energy surface (PES). Since reasonably accurate PESs are now available from quantum chemical calculations, a great deal of chemistry can, in principle, be predicted using existing techniques. We describe a few algorithms for finding low-energy exit channels from a well in a PES without foreknowledge of the products. Several illustrative applications are provided, including: (1) unimolecular rearrangement of benzocyclohex-1-en-3-yne and (2) bimolecular reaction between ammonia and dichlorosilane. These two systems were chosen because their reactions were previously found to have been predicted incorrectly. In both cases, the correct mechanisms are recovered using isopotential searching strategies.
Citation
Journal of Physical Chemistry A
Volume
104
Issue
No. 11
Pub Type
Journals
Keywords
chemical reaction, isopotential, pyrolysis, quantum chemistry, reaction mechanism, thermolysis
Citation
Irikura, K.
and Johnson, R.
(1999),
Predicting Unexpected Chemical Reactions by Isopotential Searching, Journal of Physical Chemistry A
(Accessed November 14, 2024)