A reciprocal-space formulation of surface hopping

Area of Science:

• Computational chemistry
• Materials science
• Quantum dynamics

Background:

• Surface hopping is successful for localized electronic excitations.
• Its application to band-like materials is limited.
• Existing methods struggle with delocalized electronic properties.

Purpose of the Study:

• To develop a reciprocal-space formulation of surface hopping.
• To enable efficient simulation of band-like electronic phenomena.
• To extend surface hopping to materials science applications.

Main Methods:

• Formulation of fewest-switches surface hopping in reciprocal space.
• Solving quantum and classical equations of motion in reciprocal coordinates.
• Truncation of the Brillouin zone for efficiency.

Main Results:

• Demonstrated formal equivalence between real-space and reciprocal-space surface hopping.
• Validated accuracy against established methods (Holstein, Peierls models).
• Showcased compatibility with band structure calculations.

Conclusions:

• Reciprocal-space surface hopping efficiently describes band-like electronic phenomena.
• The method is readily integrable into existing surface hopping frameworks.
• Opens new avenues for simulating excited-state dynamics in materials.