Dynamical Consequences of Nontrivial Topology of Molecular Conical Intersections

Abstract:The topology of the electronic structure for an avoided crossing and a conical intersection (CI) is different and is characterized by the presence of the geometric phase in the electronic wavefunction in the latter. Using the linear Jahn-Teller model, we show that an avoided crossing can be created from the conical intersection while preserving the nontrivial topology of the latter by adding a Pauli $\sigma_y$ term to the Hamiltonian. Analogously to solid state systems, we derive a half-integer topological invariant as the integral of the Berry curvature over the CI nuclear branching space. We investigate the influence of electronic topology on chemical dynamics by conducting fewest-switches surface hopping simulations and find distinct hopping rates on identical eigensurfaces but with different topologies. Our work extends the influence of topology on molecular excited state dynamics beyond the Berry phase that can be practically realized through electron-nuclear and spin-orbit coupling.

Chemical Physics (physics.chem-ph); Quantum Physics (quant-ph)

arXiv:2608.24864 [physics.chem-ph]

(or arXiv:2608.24864v1 [physics.chem-ph] for this version)

https://doi.org/10.48550/arXiv.2608.24864 Focus to learn more arXiv-issued DOI via DataCite (pending registration)

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