biostudies-literatureChen JNational Natural Science Foundation of ChinaNational Natural Science Foundation of China (National Science Foundation of China)4039https://www.ebi.ac.uk/biostudies/studies/S-EPMC6168487biostudies-literatureUnknown9(1)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 CH₃OH/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.Nature communicationsVibrational control of selective bond cleavage in dissociative chemisorption of methanol on Cu(111).PMC61684872157320321722306Chen JZhang YJiang BZhou XfalseVibrational control of selective bond cleavage in dissociative chemisorption of methanol on Cu(111).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 CH₃OH/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.2018-01-01T00:00:00Z2018 Oct2024-11-08T11:29:29.38Z2019-03-26T23:58:38ZS-EPMC61684873027947910.1038/s41467-018-06478-6