Harnessing work-function-driven rotational steering for quantum state control in HCl dissociation on bimetallic...

Area of Science:

• Heterogeneous catalysis
• Surface science
• Quantum dynamics

Background:

• Dissociative chemisorption of heteronuclear molecules is key in heterogeneous catalysis.
• Controlling reactivity with rotational excitation remains a challenge, unlike vibrational effects.

Purpose of the Study:

• Investigate the role of rotational excitation in HCl dissociation on bimetallic surfaces.
• Develop a predictive design principle for rotational enhancement in catalysis.

Main Methods:

• Six-dimensional quantum dynamics simulations.
• Modeling HCl dissociation on Ag/Pt(111) and Cu/Pt(111) bimetallic surfaces.

Main Results:

• Observed unprecedented rotational enhancement, with efficacies of ~225 on Ag/Pt(111) and ~56 on Cu/Pt(111).
• Discovered that interfacial charge transfer, driven by work function differences, creates a unique potential energy landscape.
• Established a quantitative principle: rotational efficacy scales with work function difference and is modulated by surface strain.

Conclusions:

• Rotational effects depend on the global potential energy surface topography, distinct from transition state localized mechanisms.
• Rotation can precisely steer catalytic reactivity, enabling state-selective catalyst design.
• This work advances a new paradigm for designing catalysts with targeted functions.