Deformation Potentials: Towards a Systematic Way beyond the Atomic Fragment Approach in Orbital-Free Density Functional Theory

This work presents a method to move beyond the recently introduced atomic fragment approximation. Like the bare atomic fragment approach, the new method is an ab initio, parameter-free, orbital-free implementation of density functional theory based on the bifunctional formalism that treats the potential and the electron density as two separate variables, and provides access to the Kohn–Sham Pauli kinetic energy for an appropriately chosen Pauli potential. In the present ansatz, the molecular Pauli potential is approximated by the sum of the bare atomic fragment approach, and a so-called deformation potential that takes the interaction between the atoms into account. It is shown that this model can reproduce the bond-length contraction due to multiple bonding within the list of second-row homonuclear dimers. The present model only relies on the electron densities of the participating atoms, which themselves are represented by a simple monopole expansion. Thus, the bond-length contraction can be rationalized without referring to the angular quantum numbers of the participating atoms.

Equilibrium Bond Lengths from Orbital-Free Density Functional Theory

This work presents an investigation to model chemical bonding in various dimers based on the atomic fragment approach. The atomic fragment approach is an ab-initio, parameter-free implementation of orbital-free density functional theory which is based on the bifunctional formalism, i.e., it uses both the density and the Pauli potential as two separate variables. While providing the exact Kohn-Sham Pauli kinetic energy when the orbital-based Kohn-Sham data are used, the bifunctional formalism allows for approximations of the functional derivative which are orbital-free. In its first implementation, the atomic fragment approach uses atoms in their ground state to model the Pauli potential. Here, it is tested how artificial closed-shell fragments with non-integer electron occupation perform regarding the prediction of bond lengths of diatomics. Such fragments can sometimes mimic the electronic structure of a molecule better than groundstate fragments. It is found that bond lengths may indeed be considerably improved in some of the tested diatomics, in accord with predictions based on the electronic structure.

Discontinuous Behavior of the Pauli Potential in Density Functional Theory as a Function of the Electron Number

<div>The Pauli potential is an essential quantity in orbital-free density-functional theory (DFT) and in the exact electron factorization (EEF) method for many-electron systems. Knowledge of the Pauli potential allows the description of a system relying on the density alone, without the need to calculate the orbitals.</div><div>In this work we explore the behavior of the exact Pauli potential in finite systems as a function of the number of electrons, employing the ensemble approach in DFT. Assuming the system is in contact with an electron reservoir, we allow the number of electrons to vary continuously and to obtain fractional as well as integer values. We derive an expression for the Pauli potential for a spin-polarized system with a fractional number of electrons and find that when the electron number surpasses an integer, the Pauli potential jumps by a spatially uniform constant, similarly to the Kohn-Sham potential. The magnitude of the jump equals the Kohn-Sham gap. We illustrate our analytical findings by calculating the exact and approximate Pauli potentials for Li and Na atoms with fractional numbers of electrons.</div>

Discontinuous Behavior of the Pauli Potential in Density Functional Theory as a Function of the Electron Number

<div>The Pauli potential is an essential quantity in orbital-free density-functional theory (DFT) and in the exact electron factorization (EEF) method for many-electron systems. Knowledge of the Pauli potential allows the description of a system relying on the density alone, without the need to calculate the orbitals.</div><div>In this work we explore the behavior of the exact Pauli potential in finite systems as a function of the number of electrons, employing the ensemble approach in DFT. Assuming the system is in contact with an electron reservoir, we allow the number of electrons to vary continuously and to obtain fractional as well as integer values. We derive an expression for the Pauli potential for a spin-polarized system with a fractional number of electrons and find that when the electron number surpasses an integer, the Pauli potential jumps by a spatially uniform constant, similarly to the Kohn-Sham potential. The magnitude of the jump equals the Kohn-Sham gap. We illustrate our analytical findings by calculating the exact and approximate Pauli potentials for Li and Na atoms with fractional numbers of electrons.</div>