Interpreting ultrafast electron transfer on surfaces with a converged first-principles Newns-Anderson chemisorption...

Area of Science:

• Surface science
• Computational chemistry
• Quantum mechanics

Background:

• Understanding electronic coupling is crucial for chemisorption.
• Existing methods often lack detailed insights into electron transfer dynamics.

Purpose of the Study:

• To develop a first-principles method for calculating tunneling matrix elements.
• To compute the Newns-Anderson chemisorption function.
• To elucidate electron transfer processes at adsorbate-metal interfaces.

Main Methods:

• Projection-operator diabatization of the Kohn-Sham Hamiltonian.
• Integration of couplings over the Brillouin zone.
• Decomposition into angular momentum components.

Main Results:

• First size-convergent calculation of the Newns-Anderson chemisorption function.
• Confirmation of electron state lifetimes for Ar* on transition metals.
• Detailed insights into orbital phase interactions and resonant electron transfer.

Conclusions:

• The developed method accurately captures electron transfer dynamics.
• The hybridized d-character of transition metal surfaces plays a key role in resonant electron transfer.
• This approach provides a comprehensive understanding of adsorbate-surface electronic coupling.