Free Energy Surfaces of Transition Metal Catalyzed Reactions
Author Information
Author(s): Marc Brüssel, Philipp J. di Dio, Kilian Muñiz, Barbara Kirchner
Primary Institution: Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, University Leipzig
Hypothesis
The study investigates the free energy surfaces of two transition metal catalyzed reactions using ab initio molecular dynamics simulations.
Conclusion
The study found that the reaction barriers for the investigated reactions are low enough to allow them to occur under the selected conditions.
Supporting Evidence
- The reaction barrier for the rearrangement of a ruthenium oxoester in water was calculated to be ΔF = 59.5 ± 8.5 kJ mol−1.
- The carbon dioxide addition to a palladium complex in carbon dioxide had a barrier of ΔF = 44.9 ± 3.3 kJ mol−1.
- Simulations showed that solvent effects significantly influence the stability of the palladium carbon dioxide complex.
Takeaway
The researchers used computer simulations to understand how two chemical reactions happen and found that they can happen easily under certain conditions.
Methodology
The study employed ab initio molecular dynamics simulations using thermodynamic integration and metadynamics to calculate free energy surfaces.
Limitations
The study acknowledges that nuclear quantum effects are usually neglected in simulations, which may affect the accuracy of the free energy surfaces.
Statistical Information
Confidence Interval
± 8.5 kJ mol−1 for the ruthenium reaction; ± 6.7 kJ mol−1 for the palladium reaction; ± 2.3 kJ mol−1 for metadynamics with one variable; ± 5.9 kJ mol−1 for metadynamics with two variables.
Digital Object Identifier (DOI)
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