Geometric phase effects in excited state dynamics through a conical intersection in large molecules: N-dimensional...

Area of Science:

• Quantum Chemistry
• Chemical Physics
• Molecular Dynamics

Background:

• Geometric phase (GP) effects are crucial in nonadiabatic transitions, particularly through conical intersections (CIs).
• The N-dimensional linear vibronic coupling (ND-LVC) model provides a framework to study these phenomena.
• Understanding GP effects is essential for predicting molecular behavior in excited states.

Purpose of the Study:

• To investigate geometric phase (GP) effects in nonadiabatic transitions within an ND-LVC model.
• To analyze how parameters of the ND-LVC model influence GP effects.
• To identify conditions that lead to the diminution of GP effects.

Main Methods:

• Utilizing an ND-LVC model that transforms nonadiabatic effects into a two-dimensional (2D) subsystem.
• Analyzing the dynamics governed by the 2D subsystem, which includes ultra-fast nonadiabatic transitions through a CI.
• Examining the relationship between ND-LVC parameters and the resulting GP effects.

Main Results:

• The 2D subsystem effectively models GP effects in nonadiabatic dynamics.
• Parameters of the ND-LVC model directly influence the Hamiltonian of the 2D subsystem and thus GP effects.
• Symmetry breaking in the 2D subsystem, driven by specific ND-LVC parameters, was found to diminish GP effects.

Conclusions:

• The ND-LVC model offers a versatile platform for studying GP effects in nonadiabatic transitions.
• Careful selection of ND-LVC parameters can control and potentially minimize GP effects.
• This research provides insights into managing nonadiabatic dynamics through conical intersections.