Measuring competing outcomes of a single-molecule reaction reveals classical Arrhenius chemical kinetics

Pieter J. Keenan, Rebecca M. Purkiss, Tillmann Klamroth, Peter A. Sloan, Kristina R. Rusimova

Research output: Contribution to journalArticlepeer-review

Abstract

Programming matter one molecule at a time is a long-standing goal in nanoscience. The atomic resolution of a scanning tunnelling microscope (STM) can give control over the probability of inducing single-outcome single-molecule reactions. Here we show it is possible to measure and influence the outcome of a single-molecule reaction with multiple competing outcomes. By precise injection of electrons from an STM tip, toluene molecules are induced to react with two outcomes: switching to an adjacent site or desorption. Within a voltage range set by the electronic structure of the molecule-surface system, we see that the branching ratio between these two outcomes is dependent on the excess energy the exciting electron carries. Using known values, ab initio DFT calculations and empirical models, we conclude that this excess energy leads to a heating of a common intermediate physisorbed state and gives control over the two outcomes via their energy barriers and prefactors.

Original languageEnglish
Article number10322
JournalNature Communications
Volume15
Issue number1
Early online date28 Nov 2024
DOIs
Publication statusPublished - 28 Nov 2024

Data Availability Statement

The data that support the findings of this study are available from the University of Bath data archive49 and from the corresponding author upon request. Source data are provided with this paper.

Acknowledgements

The authors thank Dr Victoria Scowcroft for discussions and advice on the fitting procedures.

Funding

The authors thank Dr Victoria Scowcroft for discussions and advice on the fitting procedures. This work was supported by the Royal Society (No. RGS/R1/231369, K.R.R.), the Engineering and Physical Sciences Research Council (EPSRC) (No. EP/X031934/1, K.R.R. and EP/L015544/1, RMP), and by a University of Bath studentship (P.J.K.).

FundersFunder number
Royal SocietyRGS/R1/231369
Engineering and Physical Sciences Research CouncilEP/X031934/1, EP/L015544/1

Fingerprint

Dive into the research topics of 'Measuring competing outcomes of a single-molecule reaction reveals classical Arrhenius chemical kinetics'. Together they form a unique fingerprint.

Cite this