Overcoming the Pitfalls of Computing Reaction Selectivity from Ensembles of Transition States
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.
2-s2.0-85198547762
38990895
École Polytechnique Fédérale de Lausanne
École Polytechnique Fédérale de Lausanne
École Polytechnique Fédérale de Lausanne
2024-07-25
15
29
7363
7370
REVIEWED
EPFL
| Funder | Funding(s) | Grant Number | Grant URL |
EPFL | |||
Swiss National Science Foundation | |||
National Centre of Competence in Research | |||
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