English

Molecular geometric phase from the exact electron-nuclear factorization

Chemical Physics 2016-04-14 v3 Other Condensed Matter

Abstract

The Born-Oppenheimer electronic wavefunction ΦRBO(r)\Phi_R^{BO}(r) picks up a topological phase factor ±1\pm 1, a special case of Berry phase, when it is transported around a conical intersection of two adiabatic potential energy surfaces in RR-space. We show that this topological quantity reverts to a geometric quantity eiγe^{i\gamma} if the geometric phase γ=ImΦRμΦRdRμ\gamma = \oint \mathrm{Im} \langle \Phi_R |\nabla_{\mu} \Phi_R\rangle \cdot d\mathbf{R}_{\mu} is evaluated with the conditional electronic wavefunction ΦR(r)\Phi_R(r) from the exact electron-nuclear factorization ΦR(r)χ(R)\Phi_R(r)\chi(R) instead of the adiabatic function ΦRBO(r)\Phi_R^{BO}(r). A model of a pseudorotating molecule, also applicable to dynamical Jahn-Teller ions in bulk crystals, provides the first examples of induced vector potentials and molecular geometric phase from the exact factorization. The induced vector potential gives a contribution to the circulating nuclear current which cannot be removed by a gauge transformation. The exact potential energy surface is calculated and found to contain a term depending on the Fubini-Study metric for the conditional electronic wavefunction.

Keywords

Cite

@article{arxiv.1506.09193,
  title  = {Molecular geometric phase from the exact electron-nuclear factorization},
  author = {Ryan Requist and Falk Tandetzky and E. K. U. Gross},
  journal= {arXiv preprint arXiv:1506.09193},
  year   = {2016}
}
R2 v1 2026-06-22T10:03:14.186Z