Geometric phase effects in excited state dynamics through a conical intersection in large molecules: N-dimensional linear vibronic coupling model study

摘要

We investigate geometric phase (GP) effects in nonadiabatic transitionsthrough a conical intersection (CI) in an N-dimensional linear vibroniccoupling (ND-LVC) model. This model allows for the coordinate transformationencompassing all nonadiabatic effects within a two-dimensional (2D) subsystemwhile the other N-2 dimensions form a system of uncoupled harmonic oscillatorsidentical for both electronic states and coupled bi-linearly with the subsystemcoordinates. The 2D subsystem governs ultra-fast nonadiabatic dynamics throughthe CI and provides a convenient model for studying GP effects. Parameters ofthe original ND-LVC model define the Hamiltonian of the transformed 2Dsubsystem and thus influence GP effects directly. Our analysis reveals whatvalues of ND-LVC parameters can introduce symmetry breaking in the 2D subsystemthat diminishes GP effects.