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research article

Overcoming the Pitfalls of Computing Reaction Selectivity from Ensembles of Transition States

Laplaza, Ruben  
•
Wodrich, Matthew D.  
•
Corminboeuf, Clemence  
July 25, 2024
The Journal of Physical Chemistry Letters

The prediction of reaction selectivity is a challenging task for computational chemistry, not only because many molecules adopt multiple conformations but also due to the exponential relationship between effective activation energies and rate constants. To account for molecular flexibility, an increasing number of methods exist that generate conformational ensembles of transition state (TS) structures. Typically, these TS ensembles are Boltzmann weighted and used to compute selectivity assuming Curtin-Hammett conditions. This strategy, however, can lead to erroneous predictions if the appropriate filtering of the conformer ensembles is not conducted. Here, we demonstrate how any possible selectivity can be obtained by processing the same sets of TS ensembles for a model reaction. To address the burdensome filtering task in a consistent and automated way, we introduce marc, a tool for the modular analysis of representative conformers that aids in avoiding human errors while minimizing the number of reoptimization computations needed to obtain correct reaction selectivity.

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Type
research article
DOI
10.1021/acs.jpclett.4c01657
Scopus ID

2-s2.0-85198547762

PubMed ID

38990895

Author(s)
Laplaza, Ruben  

École Polytechnique Fédérale de Lausanne

Wodrich, Matthew D.  

École Polytechnique Fédérale de Lausanne

Corminboeuf, Clemence  

École Polytechnique Fédérale de Lausanne

Date Issued

2024-07-25

Published in
The Journal of Physical Chemistry Letters
Volume

15

Issue

29

Start page

7363

End page

7370

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCMD  
FunderFunding(s)Grant NumberGrant URL

EPFL

Swiss National Science Foundation

National Centre of Competence in Research

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Available on Infoscience
January 24, 2025
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/243428
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