Chemists appreciate that the rate of redox reactions can be manipulated by means of an electrical potential gradient. However, an external electric field can also be used to catalyse non-redox reactions. So-called electrostatic catalysis arises because most chemical species have some degree of polarity and so can be stabilized by an appropriately aligned electric field; when this occurs to a greater extent in transition states compared with reactants, reactions are catalysed. One way of studying of such electric field effects is through break-junction scanning tunnelling microscopy (STM) in blinking mode, as it provides a means of orienting reagents in an electric field, while providing both the means of applying a field of known strength and bias, and measuring the resulting single molecule reaction rate. Using this approach, supported by theoretical calculations, we have recently demonstrated significant electric field effects on bimolecular and unimolecular reactions, thus opening up a new approach to catalysis. Moreover, the work also implies that the electric fields present in STM experiments can have an impact on any bond breaking and related measurements. In this presentation our latest results will be presented and their implications for single molecule experiments discussed.

Electric field effects on chemical reactivity: A single molecule perspective

ACS Spring Meeting 2021

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