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Is the equilibrium composition of mechanochemical reactions predictable using computational chemistry?

Is the equilibrium composition of mechanochemical reactions predictable using computational chemistry?
Is the equilibrium composition of mechanochemical reactions predictable using computational chemistry?
The ability of computational methods to predict the structures and energetics that determine the equilibrium of solid state mechanochemical reactions has been assessed. Two previously characterised base catalysed metathesis reactions between aromatic disulfides are studied using crystal structure prediction methods and 10 lattice energy calculations that combine molecular electronic structure methods with anisotropic atom-atom potentials. We find that lattice energy searches locate three of the six crystal structures as global minima on their respective crystal energy landscapes. The remaining structures are less successfully predicted, due to problems 15 modelling relative conformational energies due to limitations of the density functional theory method for calculating intramolecular energies. Prediction of the overall reaction energies proves challenging for current methods, but the results show promise as a
base on which to build more accurate and reliable approaches.
0301-7249
41-57
Bygrave, P.J.
d9e03e4f-defd-4ddb-ae45-3cbd9c951fdc
Case, D.H.
aeaffa58-bfb7-440e-ab3a-70798b1f583b
Day, G.M.
e3be79ba-ad12-4461-b735-74d5c4355636
Bygrave, P.J.
d9e03e4f-defd-4ddb-ae45-3cbd9c951fdc
Case, D.H.
aeaffa58-bfb7-440e-ab3a-70798b1f583b
Day, G.M.
e3be79ba-ad12-4461-b735-74d5c4355636

Bygrave, P.J., Case, D.H. and Day, G.M. (2014) Is the equilibrium composition of mechanochemical reactions predictable using computational chemistry? Faraday Discussions, 170 (1), 41-57. (doi:10.1039/c3fd00162h).

Record type: Article

Abstract

The ability of computational methods to predict the structures and energetics that determine the equilibrium of solid state mechanochemical reactions has been assessed. Two previously characterised base catalysed metathesis reactions between aromatic disulfides are studied using crystal structure prediction methods and 10 lattice energy calculations that combine molecular electronic structure methods with anisotropic atom-atom potentials. We find that lattice energy searches locate three of the six crystal structures as global minima on their respective crystal energy landscapes. The remaining structures are less successfully predicted, due to problems 15 modelling relative conformational energies due to limitations of the density functional theory method for calculating intramolecular energies. Prediction of the overall reaction energies proves challenging for current methods, but the results show promise as a
base on which to build more accurate and reliable approaches.

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Accepted/In Press date: 15 January 2014
e-pub ahead of print date: 11 June 2014
Published date: 1 December 2014
Organisations: Computational Systems Chemistry

Identifiers

Local EPrints ID: 363611
URI: http://eprints.soton.ac.uk/id/eprint/363611
ISSN: 0301-7249
PURE UUID: ccaa48a7-f9a3-4a76-9e0a-d16f5c0490f7
ORCID for G.M. Day: ORCID iD orcid.org/0000-0001-8396-2771

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Date deposited: 27 Mar 2014 16:13
Last modified: 17 Dec 2019 01:38

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Contributors

Author: P.J. Bygrave
Author: D.H. Case
Author: G.M. Day ORCID iD

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