Phase-space surface hopping: nonadiabatic dynamics in a superadiabatic basis.

Area of Science:

• Quantum Chemistry
• Computational Chemistry
• Theoretical Chemistry

Background:

• Strong nonadiabatic coupling presents challenges for traditional surface hopping algorithms.
• Existing methods often struggle to accurately capture dynamics in systems with significant electronic-vibrational interactions.

Purpose of the Study:

• To develop a novel phase-space surface hopping algorithm.
• To improve the accuracy of simulating quantum dynamics in systems with strong nonadiabatic coupling.

Main Methods:

• Constructed a phase-space surface hopping algorithm using a nuclear phase-space coordinate-dependent electronic basis.
• Derived generalized Hamilton's equations of motion for nuclear dynamics.
• Compared the phase-space method against position-space surface hopping for a model system.

Main Results:

• The phase-space surface hopping algorithm captures physical effects missed by traditional methods.
• Demonstrated superior accuracy of the phase-space method compared to position-space methods for strong nonadiabatic coupling.
• The phase-space adiabatic basis is identified as a first-order superadiabatic correction to the conventional basis.

Conclusions:

• The developed phase-space surface hopping algorithm offers a more accurate approach for simulating quantum dynamics.
• This method is particularly advantageous for systems exhibiting strong nonadiabatic coupling.
• The findings advance the field of computational quantum dynamics and molecular simulations.