Chemical reactivity in spin-polarized density functional theory

Abstract

Spin-polarized density functional theory is used to analyze chemical reactivity from a more general point of view, which distinguishes between the changes produced by charge transfer between the interacting species (changes in the total number of electrons, N = + TVj where f refers to spin-up or a and , to spin-down or ß) and the changes produced by the redistribution of the electronic density of each of the interacting species (changes in the spin number, Ns = Af -7V|). It is found that the response of the system to changes in N and the external potential is given in terms of the chemical potential, the hardness, the electronic density, and the Fukui function, while the response of the system to changes in 7VS and an external magnetic field is given in terms of a new set of parameters which we have named the spin potential, the spin hardness, the spin density, and the spin Fukui function. Making use of the Kohn-Sham approach to density functional theory, it is shown that the generalized Fukui functions can be reduced to a set of spin-polarized classical frontier orbitals by imposing frozen core approximations.

Chemical reactivity indexes in density functional theory

“…168, 169 Galvan et al also introduced spin hardnesses and related Fukui functions. 168,170 The changes of N keeping N constant are associated S with the transit through different valence states so that -a ground-state property-is related to S the energies of promoted states.…”

An explicit approach to conceptual density functional theory descriptors of arbitrary order

“…In this way, we derive explicit expressions for global, local and non-local reactivity descriptors up to arbitrary order, many of which are reported here for the first time. The framework can be extended to spinresolved reactivity indicators [15][16][17] in the standard way, but this extension will not be discussed here. [18,19].…”

Minimizers for open-shell, spin-polarised Kohn–Sham equations for non-relativistic and quasi-relativistic molecular systems

“…A spin-polarised theory, like the unrestricted Kohn-Sham model, is one which accounts for an excess of spin-up (or spin-down) electrons. Numerous physicists and chemists working in DFT have realised that spin-polarised theories can lead to improved approximations [34,18,31] of molecular bonding energies, kinetic energies, and other quantities of interest, e.g., the spin potential [12,13].…”