Vibrational control of selective bond cleavage in dissociative chemisorption of methanol on Cu(111).
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 30279479.
- Also identified by DOI 10.1038/s41467-018-06478-6 and PMC identifier 6168487.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Controlling product branching ratios in a chemical reaction represents a desired but difficult achievement in chemistry. In this work, we demonstrate the first example of altering the branching ratios in a multichannel reaction, i.e., methanol dissociative chemisorption on Cu(111), via selectively exciting specific vibrational modes. To this end, we develop a globally accurate full-dimensional potential energy surface for the CH<sub>3</sub>OH/Cu(111) system and perform extensive vibrational state-selected molecular dynamics simulations. Our results show that O-H/C-H/C-O stretching vibrational excitations substantially enhance the respective bond scission processes, representing extraordinary bond selectivity. At a given total energy, the branching ratio of C-O/C-H dissociation can increase by as large as 100 times by exciting the C-O stretching mode which possesses an unprecedentedly strong vibrational efficacy on reactivity. This vibrational control can be realized by the well-designed experiment using a linearly polarized laser.