Electronic Vector Potential from the Exact Factorization of a Complex Wavefunction

Abstract

We generalize the definitions of local scalar potentials named vkin and vN−1, which are relevant to properly describe phenomena such as molecular dissociation with density‐functional theory, to the case in which the electronic wavefunction corresponds to a complex current‐carrying state. In such a case, an extra term in the form of a vector potential appears which cannot be gauged away. Both scalar and vector potentials are introduced via the exact factorization formalism which allows us to express the given Schrödinger equation as two coupled equations, one for the marginal and one for the conditional amplitude. The electronic vector potential is directly related to the paramagnetic current density carried by the total wavefunction and to the diamagnetic current density in the equation for the marginal amplitude. An explicit example of this vector potential in a triplet state of two non‐interacting electrons is showcased together with its associated circulation, giving rise to a non‐vanishing geometric phase. Some connections with the exact factorization for the full molecular wavefunction beyond the Born‐Oppenheimer approximation are also discussed.

Simulations of photoinduced processes with the exact factorization: State of the art and perspectives

“…[ 118,[120][121][122][123][124][125][126] for an overview of the topics tackled by various authors employing the time-independent formulation of the exact factorization. In addition, alternative viewpoints have been proposed to study electron-nuclear [126][127][128][129][130][131][132] , electronelectron [133][134][135][136] and photon-electron-nuclear [137][138][139][140][141][142] systems.…”