Exact factorization-based density functional theory of electrons and nuclei

TL;DR

This paper develops an exact factorization-based density functional theory for electrons and nuclei, introducing a variational functional involving electronic density, nuclear wavefunction, and geometric potentials, with applications to the Jahn-Teller model.

Contribution

It introduces a new variational framework for electron-nuclear systems that incorporates geometric potentials and can be solved self-consistently, advancing the theoretical understanding of molecular systems.

Findings

Derived a variational functional involving electronic density, nuclear wavefunction, and geometric potentials.

Formulated self-consistent equations including conditional Kohn-Sham and Schrödinger equations.

Applied the theory to the Jahn-Teller model demonstrating its practical utility.

Abstract

The ground state energy of a system of electrons and nuclei is proven to be a variational functional of the conditional electronic density $n_R(\mathbf{r})$, the nuclear wavefunction $\chi(R)$ and an induced vector potential $A_{\mu}(R)$ and quantum geometric tensor $\mathcal{T}_{\mu\nu}(R)$ derived from the conditional electronic wavefunction $\Phi_R(r)$ over nuclear configuration space, where $r=\mathbf{r}_1,\mathbf{r}_2,\ldots$ are electronic coordinates and $R=\mathbf{R}_1,\mathbf{R}_2,\ldots$ are nuclear coordinates. The ground state $(n_R,\chi,A_{\mu},\mathcal{T}_{\mu\nu})$ can be calculated by solving self-consistently (i) conditional Kohn-Sham equations containing an effective potential $v_{\rm s}(\mathbf{r})$ that depends parametrically on $R$, (ii) the Schr\"odinger equation for $\chi(R)$ and (iii) Euler-Lagrange equations that determine $\mathcal{T}_{\mu\nu}$. The theory is applied to the $E\otimes e$ Jahn-Teller model.