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We present a phase-space electronic Hamiltonian ĤPS (parameterized by both nuclear position X and momentum P) that boosts each electron into the moving frame of the nuclei that are closest in real space. The final form for the phase space Hamiltonian does not assume the existence of an atomic orbital basis, and relative to standard Born–Oppenheimer theory, the newly proposed one-electron operators can be expressed directly as functions of electronic and nuclear positions and momentum. We show that (i) quantum–classical dynamics along such a Hamiltonian maintains momentum conservation and that (ii) diagonalizing such a Hamiltonian can recover the electronic momentum and electronic current density reasonably well. In conjunction with other reports in the literature that such a phase-space approach can also recover vibrational circular dichroism spectra, we submit that the present phase-space approach offers a testable and powerful approach to post-BO electronic structure theory. Moreover, the approach is inexpensive and can be immediately applied to simulations of chiral induced spin selectivity experiments (where the transfer of angular momentum between nuclei and electrons is considered critical). 

Modern electronic structure theory is built around the Born–Oppenheimer approximation and the construction of an electronic Hamiltonian Ĥel(X) that depends on the nuclear position X (and not the nuclear momentum P). In this article, using the well-known theory of electron translation (Γ′) and rotational (Γ″) factors to couple electronic transitions to nuclear motion, we construct a practical phase-space electronic Hamiltonian that depends on both nuclear position and momentum, ĤPS(X,P). While classical Born–Oppenheimer dynamics that run along the eigensurfaces of the operator Ĥel(X) can recover many nuclear properties correctly, we present some evidence that motion along the eigensurfaces of ĤPS(X,P) can better capture both nuclear and electronic properties (including the elusive electronic momentum studied by Nafie). Moreover, only the latter (as opposed to the former) conserves the total linear and angular momentum in general.