Exponential convergence of the local diabatic representation for nonadiabatic eigenvalue problems.
1Department of Chemistry and Department of Physics, Westlake University, Hangzhou, Zhejiang 310030, China. gubing@westlake.edu.cn.
Physical Chemistry Chemical Physics : PCCP
|April 7, 2026
Summary
The discrete variable local diabatic representation (LDR) offers a robust framework for simulating conical intersection dynamics. LDR demonstrates superior convergence for complex systems compared to traditional methods.
Area of Science:
- Quantum Chemistry
- Theoretical Chemistry
- Chemical Dynamics
Background:
- Accurate simulation of molecular dynamics, especially at conical intersections, is crucial for understanding chemical reactions.
- Traditional methods like the Born-Huang ansatz face convergence challenges due to derivative couplings.
Purpose of the Study:
- To investigate the convergence properties of the discrete variable local diabatic representation (LDR).
- To compare LDR performance against the Born-Huang ansatz and crude adiabatic representation for eigenvalue problems.
Main Methods:
- Utilized coupled oscillator models and a conical intersection model.
- Assessed convergence with respect to nuclear grid points and electronic states.
- Compared LDR with Born-Huang and crude adiabatic representations.
Main Results:
- LDR shows similar convergence to exact Born-Huang for weak vibronic couplings.
- LDR converges significantly faster than Born-Huang for strong vibronic couplings.
- LDR remains accurate and converges exponentially for conical intersections where Born-Huang fails.
Conclusions:
- LDR provides a divergence-free and highly accurate framework for conical intersection dynamics.
- LDR offers a more efficient alternative to traditional methods, especially for complex systems.
- Diagonal Born-Oppenheimer corrections and second-order derivative couplings are important in the Born-Huang framework.
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