Quantum corrected Langevin dynamics for adsorbates on metal surfaces interacting with hot electrons

Area of Science:

• Surface science
• Computational chemistry
• Quantum dynamics

Background:

• Langevin dynamics is used to model adsorbate interactions with electron reservoirs.
• Classical approximations in initial conditions can lead to inaccuracies.
• Understanding quantum effects is vital for surface processes.

Purpose of the Study:

• To investigate the necessity of quantized initial conditions in Langevin dynamics.
• To compare results from quantized vs. classical initial conditions.
• To assess the impact on adsorbate desorption and vibrational states.

Main Methods:

• Developed a method to derive quantum probabilities from classical phase space distributions.
• Employed ab initio calculations for frictional tensors and potential energy surfaces.
• Utilized a quantum mechanical master equation for comparison.

Main Results:

• Classical and quasiclassical initial conditions yield incorrect results at short timescales.
• Quantized initial conditions closely match the quantum master equation approach.
• Demonstrated significant effects on desorption probability and vibrational state distributions for CO/Cu(100).

Conclusions:

• Quantized initial conditions are essential for accurate Langevin dynamics of adsorbates.
• The inclusion of quantum effects is critical for precise modeling of surface phenomena.
• This approach provides a more reliable method for predicting adsorbate behavior.