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Chemical reactions modulated by mechanical stress: Extended Bell theory
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10.1063/1.3656367
/content/aip/journal/jcp/135/16/10.1063/1.3656367
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/16/10.1063/1.3656367
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

Conrotatory pathway for electrocyclic ring-opening of (a) cis and (b) trans 1,2-dimethylbenzocyclobutene. The force applied to two carbons lowers the reaction barrier if the distance R ij between these atoms is longer in the transition state than it is in the reactant state.

Image of FIG. 2.
FIG. 2.

Simple one-dimensional model of a chemical reaction modulated by a mechanical force.19,20 The force lowers the reaction barrier and shifts the reactant and transition-state conformations toward one another.

Image of FIG. 3.
FIG. 3.

The conrotatory electrocyclic ring-opening of (a) cis 1,2-dimethylbenzocyclobutene leads to the cis, trans diene A and (b) trans 1,2-dimethylbenzocyclobutene leads to the trans, trans diene B. The curved arrows indicate the direction in which the orbitals associated with the C1–C2 σ-bond open. Hydrogen atoms are implicit in the structure, including at the atoms C1 and C2.

Image of FIG. 4.
FIG. 4.

Comparison of the force dependence of the reaction barrier obtained by different methods for (a) cis and (b) trans 1,2-dimethylbenzocyclobutene. Solid line: EBT. Dotted line: Bell's formula. Dashed line: “exact” result obtained from constrained structure optimization.

Image of FIG. 5.
FIG. 5.

The reactant (a) and transition-state (b) energies of cis-1,2-dimethylbenzocyclobutene as a function of the extension R ij . The energy in each case is measured relative to its respective minimum value. Solid lines show the harmonic approximation (Eqs. (16) and (18)), while the solid symbols represent results of constrained optimization, as described in Sec. III.

Image of FIG. 6.
FIG. 6.

The reactant (a) and transition-state (b) energies of trans-1,2-dimethylbenzocyclobutene as a function of the extension R ij . The energy in each case is measured relative to its respective minimum value. Solid lines show the harmonic approximation (Eqs. (16) and (18)), while the solid symbols represent results of constrained optimization, as described in Sec. III.

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/content/aip/journal/jcp/135/16/10.1063/1.3656367
2011-10-27
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Chemical reactions modulated by mechanical stress: Extended Bell theory
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/16/10.1063/1.3656367
10.1063/1.3656367
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