Critical Assessment of Curvature-Driven Surface Hopping Algorithms
Tomáš Jíra1, Jiří Janoš1, Petr Slavíček1
1Department of Physical Chemistry, University of Chemistry and Technology, Technická 5, Prague 6 16628, Czech Republic.
Journal of Chemical Theory and Computation
|September 16, 2025
Summary
Curvature-driven surface hopping methods struggle with complex molecular dynamics involving multiple electronic states or surface discontinuities. The Landau-Zener surface hopping (LZSH) method offers a more robust alternative, especially when nonadiabatic couplings are unavailable.
Area of Science:
- Computational Chemistry
- Quantum Dynamics
- Molecular Modeling
Background:
- Trajectory surface-hopping (TSH) is a key method for simulating nonadiabatic molecular dynamics.
- Curvature-driven TSH schemes are popular due to their compatibility with machine learning models providing local potential energy surface (PES) information.
Purpose of the Study:
- To critically assess the limitations of curvature-driven TSH algorithms.
- To extend and improve the Landau-Zener surface hopping (LZSH) method for complex systems.
- To compare the performance of curvature-driven TSH and LZSH methods.
Main Methods:
- Analysis of curvature-driven TSH in scenarios with multiple coupled electronic states, trivial crossings, and PES discontinuities.
- Extension of the Landau-Zener surface hopping (LZSH) method for systems beyond two electronic states.
- Benchmarking on low- and higher-dimensional model Hamiltonians and ab initio calculations of molecular systems.
Main Results:
- Curvature-driven TSH qualitatively captures dynamics but shows limitations in challenging scenarios.
- No regime was found where curvature-driven TSH outperforms LZSH, particularly with trivial crossings, multistate crossings, or discontinuities.
- Extended LZSH method demonstrates enhanced robustness and performance.
Conclusions:
- Curvature-driven TSH methods have significant limitations in accurately describing complex nonadiabatic dynamics.
- The Landau-Zener surface hopping (LZSH) method is a more reliable and robust approach, especially when nonadiabatic couplings are not readily available.
- LZSH is recommended for simulations involving challenging crossings and discontinuities in potential energy surfaces.
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