Theoretical Approaches for Understanding the Interplay Between Stress and Chemical Reactivity

Abstract

The use of mechanical stresses to induce chemical reactions has attracted significant interest in recent years. Computational modeling can play a significant role in developing a comprehensive understanding of the interplay between stresses and chemical reactivity. In this review, we discuss techniques for simulating chemical reactions occurring under mechanochemical conditions. The methods described are broadly divided into techniques that are appropriate for studying molecular mechanochemistry and those suited to modeling bulk mechanochemistry. In both cases, several different approaches are described and compared. Methods for examining molecular mechanochemistry are based on exploring the force-modified potential energy surface on which a molecule subjected to an external force moves. Meanwhile, it is suggested that condensed phase simulation methods typically used to study tribochemical reactions, i.e., those occurring in sliding contacts, can be adapted to study bulk mechanochemistry.

Perspective: Mechanochemistry of biological and synthetic molecules

“…To this end, several computational methods have been proposed (and reviewed in Ref. 102). Those include explicit incorporation of the force term into a PES 21,[106][107][108] (as in Eq.…”

First principles study of organophosphorus additives in boundary lubrication conditions: Effects of hydrocarbon chain length

“…To our knowledge, no theoretical investigations on the impact of the chain length on the additive functionality in BL have been previously reported in the literature. Nevertheless, computational studies can play a significant role in developing a comprehensive understanding on the interplay between stress and chemical reactivity, to investigate the rupture forces of bonds, the effect of chain length when molecules or polymers undergo stress‐assisted structural changes …”

“…To our knowledge, no theoretical investigations on the impact of the chain length on the additive functionality in BL have been previously reported in the literature. Nevertheless, computational studies can play a significant role in developing a comprehensive understanding on the interplay between stress and chemical reactivity, 11,[22][23][24][25] to investigate the rupture forces of bonds, 26 the effect of chain length when molecules or polymers undergo stress-assisted structural changes. 22 Here, we apply first principles calculations to study the molecular adsorption, interface confinement, load-induced enthalpy increase, and subsequent molecular dissociation of TMPi and TBPi additives at the iron interface.…”

The Challenges and Opportunities of Contemporary Polymer Mechanochemistry

“…The more ac hain is stretched, the more the kinetica nd thermodynamic stabilities of its constituent monomers changes. [11][12][13] Consequently,c hemists discuss polymer mechanochemistry in terms of effectso ff orce on reactivitya nd contrasts are often drawn in the literature between force and other experimentalv ariables that affect reaction rates, mecha-nisms and energies, including temperature and (more rarely) pressure, solvento re lectromagnetic fields. This fragmentation lowers the density of bonds across which the load distributes and thust he capacityo ft he material to withstand furtherl oading, ultimately resulting in materialf ailure.…”

“…This fragmentation lowers the density of bonds across which the load distributes and thust he capacityo ft he material to withstand furtherl oading, ultimately resulting in materialf ailure. [11][12][13] Consequently,c hemists discuss polymer mechanochemistry in terms of effectso ff orce on reactivitya nd contrasts are often drawn in the literature between force and other experimentalv ariables that affect reaction rates, mecha-nisms and energies, including temperature and (more rarely) pressure, solvento re lectromagnetic fields. The role of mechanochemistry in facilitatingm aterial failure and( potentially)p reventingi te xplains the contemporary interest in the field from materials scientists and engineers.…”