Implementing the mechanical force into the conceptual DFT framework: understanding and predicting molecular mechanochemical properties

文献情報

出版日 2019-03-20

DOI 10.1039/C8CP07349J

インパクトファクター 3.676

著者

Tom Bettens, Mercedes Alonso, Paul Geerlings, Frank De Proft

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要旨

In molecular mechanochemistry, the chemical properties of a reactant system are modified through the absorption of mechanical energy at the single molecular level, as opposed to thermochemistry (heat), electrochemistry (electrical current) and photochemistry (light). In this proof-of-concept paper, we present a theoretical approach to rationalize and predict the change in chemical properties and concepts when an external stretching force, Fext, is applied to a chemical bond. By considering perturbations to the total molecular energy due to Fext, a series of mechanochemical response indices are obtained within the framework of conceptual density functional theory (DFT). Trends in these indices monitoring the change in hardness and electrophilicity among others, were rationalized for a number of diatomic molecules in terms of the ground-state geometry and the frontier molecular orbitals of the molecule. Finally, we present a set of rules that can be easily adopted for polyatomic molecules to predict the changing chemical reactivity of single molecules when subjected to an external force.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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