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Vibrational control of selective bond cleavage in dissociative chemisorption of methanol on Cu(111).

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 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.

SUBMITTER: Chen J

PROVIDER: S-EPMC6168487 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Vibrational control of selective bond cleavage in dissociative chemisorption of methanol on Cu(111).

Chen Jialu J Zhou Xueyao X Zhang Yaolong Y Jiang Bin B

Nature communications 20181002 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 CH<sub>3</sub>OH/Cu(111) system and perform extensive vibrational stat ...[more]

PMID: 30279479

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Project description:Accurate barriers for rate controlling elementary reactions on metal surfaces are key to understanding, controlling, and predicting the rate of heterogeneously catalyzed processes. While barrier heights for gas phase reactions have been extensively benchmarked, dissociative chemisorption barriers for the reactions of molecules on metal surfaces have received much less attention. The first database called SBH10 and containing 10 entries was recently constructed based on the specific reaction parameter approach to density functional theory (SRP-DFT) and experimental results. We have now constructed a new and improved database (SBH17) containing 17 entries based on SRP-DFT and experiments. For this new SBH17 benchmark study, we have tested three algorithms (high, medium, and light) for calculating barrier heights for dissociative chemisorption on metals, which we have named for the amount of computational effort involved in their use. We test the performance of 14 density functionals at the GGA, GGA+vdW-DF, and meta-GGA rungs. Our results show that, in contrast with the previous SBH10 study where the BEEF-vdW-DF2 functional seemed to be most accurate, the workhorse functional PBE and the MS2 density functional are the most accurate of the GGA and meta-GGA functionals tested. Of the GGA+vdW functionals tested, the SRP32-vdW-DF1 functional is the most accurate. Additionally, we found that the medium algorithm is accurate enough for assessing the performance of the density functionals tested, while it avoids geometry optimizations of minimum barrier geometries for each density functional tested. The medium algorithm does require metal lattice constants and interlayer distances that are optimized separately for each functional. While these are avoided in the light algorithm, this algorithm is found not to give a reliable description of functional performance. The combination of relative ease of use and demonstrated reliability of the medium algorithm will likely pave the way for incorporation of the SBH17 database in larger databases used for testing new density functionals and electronic structure methods.

Dataset Information

Vibrational control of selective bond cleavage in dissociative chemisorption of methanol on Cu(111).

Publications

Vibrational control of selective bond cleavage in dissociative chemisorption of methanol on Cu(111).

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