Mechanically induced chemistry: first principles simulation
This review surveys first principles quantum chemistry studies on bond rupture, as probed in single molecule experiments. The processes which occur around the rupture event have recently become of interest to the development of mechanochemistry, where selective mechanical activation of reactions could provide a basis for new synthetic routes. A full description of the electronic structure is essential in theoretical approaches to describing rupture mechanisms. The theoretical methods can be divided into two: one in which molecules are deformed by constraining the geometry or applying force and quantum chemistry calculations are used to map a potential surface, and first principles molecular dynamics in which the evolution of the electronic structure during rupture and subsequent reactions can be followed. Inclusion of solvent molecules and substrates in the first principles molecular dynamics simulations allows the accurate determination of mechanically activated reaction pathways. It is anticipated that a greater experimental and theoretical effort towards understanding the role of force in manipulating strong covalent interactions will make precise mechanical control of reactions an interesting new area for development.