English

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

Chemical Physics 2017-09-13 v1 Quantum Physics

Abstract

We investigate geometric phase (GP) effects in nonadiabatic transitions through a conical intersection (CI) in an N-dimensional linear vibronic coupling (ND-LVC) model. This model allows for the coordinate transformation encompassing all nonadiabatic effects within a two-dimensional (2D) subsystem while the other N-2 dimensions form a system of uncoupled harmonic oscillators identical for both electronic states and coupled bi-linearly with the subsystem coordinates. The 2D subsystem governs ultra-fast nonadiabatic dynamics through the CI and provides a convenient model for studying GP effects. Parameters of the original ND-LVC model define the Hamiltonian of the transformed 2D subsystem and thus influence GP effects directly. Our analysis reveals what values of ND-LVC parameters can introduce symmetry breaking in the 2D subsystem that diminishes GP effects.

Keywords

Cite

@article{arxiv.1707.08266,
  title  = {Geometric phase effects in excited state dynamics through a conical intersection in large molecules: N-dimensional linear vibronic coupling model study},
  author = {Jiaru Li and Loïc Joubert-Doriol and Artur F. Izmaylov},
  journal= {arXiv preprint arXiv:1707.08266},
  year   = {2017}
}

Comments

in press: J. Chem. Phys. 2017

R2 v1 2026-06-22T20:57:35.222Z