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http://hdl.handle.net/2445/170096
Title: | Benchmarking of DFT methods using experimental free energies and volumes of activation for the cycloaddition of alkynes to cuboidal Mo3S4 clusters |
Author: | Pedrajas, Elena Pino Chamorro, José A. Ferrer García, Montserrat Fernández Trujillo, M. Jesús Llusar, Rosa Martínez López, Manuel, 1957- Basallote, Manuel G. Algarra, Andrés G. |
Keywords: | Cinètica química Mecanismes de reacció (Química) Chemical kinetics Reaction mechanisms (Chemistry) |
Issue Date: | 25-Jun-2020 |
Publisher: | Wiley |
Abstract: | Here, the kinetics of the concerted [3 + 2] cycloaddition reaction between the [Mo3(μ3‐S)(μ‐S)3Cl3(dmen)3]+ (dmen = N,N′‐dimethyl‐ethylenediamine) ([1]+) cluster and various alkynes to form dithiolene derivatives is thoroughly studied, with measurements at different temperatures and pressures allowing the determination of the free energies and volumes of activation. These parameters, together with the available single‐crystal X‐ray diffraction structures, are used to test a number of commonly used density functional theory (DFT) methods from Jacob's ladder, as well as the effects associated with the size of the basis sets, the way in which solvent effects are taken into account, or the inclusion of dispersion effects. Overall, a protocol that leads to average deviations between experimental and computed ΔV and ΔG values similar to the uncertainty of the experimental measurements is obtained. |
Note: | Versió postprint del document publicat a: https://doi.org/10.1002/qua.26353 |
It is part of: | International Journal of Quantum Chemistry, 2020, vol. 120, num. 19, p. e26353 |
URI: | http://hdl.handle.net/2445/170096 |
Related resource: | https://doi.org/10.1002/qua.26353 |
ISSN: | 0020-7608 |
Appears in Collections: | Articles publicats en revistes (Química Inorgànica i Orgànica) |
Files in This Item:
File | Description | Size | Format | |
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701243.pdf | 1.15 MB | Adobe PDF | View/Open |
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