Charge Delocalization Induces Reaction in Molecular Chains at a Surface


  • We are grateful for financial support from the Natural Sciences and Engineering Research Council of Canada (NSERC), the Xerox Research Centre Canada (XRCC), and the Canadian Institute for Advanced Research (CIFAR). Computations were performed on the Tightly Coupled System (TCS) supercomputer at the SciNet. SciNet is funded by: the Canada Foundation for Innovation under the auspices of Compute Canada; the Government of Ontario; Ontario Research Fund—Research Excellence; and the University of Toronto. We thank Prof. Hong Guo at McGill University and Prof. Wei Ji at Renmin University of China for helpful discussion of our ab initio calculations.


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The molecular dynamics of an electron-induced reaction in a self-assembled molecular chain of four dimethyldisulfide molecules on Au(111) are studied (see figure, S[BOND]S bonds highlighted). Charge delocalization weakens all the S[BOND]S bonds causing a concurrent reaction along the entire chain (middle). All the original S[BOND]S bonds are broken and new S[BOND]S bonds form giving three altered S[BOND]S bonds and two chemisorbed thiyl radicals (bottom).