Electronic–nuclear entanglement in Born–Oppenheimer wave functions and beyond

We analyze the entanglement between electronic and nuclear motions in molecular wave functions widely used by theoretical chemists, namely, (i) Born-Oppenheimer factorization in the adiabatic picture, (ii) the transformation into a diabatic picture, (iii) the use of a Born-Huang expansion, and (iv) the eigenfunction of the full molecular Hamiltonian. Our showcase is based on two one-electron one-dimensional molecular Hamiltonians (H2+ and the Shin-Metiu model). We find that within the Born-Oppenheimer approximation, any molecular state (although factorizable) is always entangled, and its entanglement content may be assessed by the variation of the electronic wave function along the different nuclear geometries, with the nuclear wave function indeed playing the role of a tester. The presence of avoided crossings among the adiabatic potential energy curves brings about dramatic changes in the entanglement content of the wave function: sharp avoided crossings favor a diabatic picture (real crossings between potential energy curves), while in broad avoided crossings, the adiabatic picture prevails. The total eigenfunction of the molecular Shin-Metiu Hamiltonian indicates that nuclear densities accommodate well within the diabatic curves for strong adiabatic couplings but within adiabatic curves for weak ones. Consequently, we find that the electron-nuclei entanglement content is a valid witness to unveil strong or weak nonadiabatic couplings in molecules. In terms of entanglement, we also find that the Born-Huang expansion, based on Born-Oppenheimer adiabatic electronic states, does not provide a correct trend of entanglement compared with that of the total molecular eigenfunction, thus indicating a very slow convergence of this expansion.