Towards bond selective chemistry from first principles: methane on metal surfaces

Area of Science:

• Surface Science
• Chemical Physics
• Computational Chemistry

Background:

• Controlling bond-selective chemical reactivity is crucial for diverse applications.
• Understanding reactivity at surfaces informs catalyst design and chemical synthesis.

Purpose of the Study:

• To investigate the bond-selective reactivity of methane and its isotopologues on Ni(111) and Pt(111) surfaces.
• To elucidate the mechanisms behind experimentally observed C-H bond selectivity via vibrational excitation.
• To explore the impact of translational energy on selectivity and identify conditions for C-D bond activation.

Main Methods:

• First-principles calculations
• Molecular dynamics simulations
• Analysis of methane and deuterated isotopologues (CH(4-x)D(x), x=0-4)

Main Results:

• Reproduced experimentally observed full C-H bond selectivity through mode-specific vibrational excitation.
• Explained the origin of this bond selectivity.
• Predicted the influence of molecular translational energy on reactivity.
• Identified conditions for activating the less reactive C-D bond.

Conclusions:

• Vibrational excitation is key to achieving high bond selectivity in methane reactions on transition metals.
• Translational energy plays a significant role and can be tuned for specific bond activation.
• These findings offer insights for designing targeted chemical reactions at surfaces.