Local SIC

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PZSIC equation

$E^{PZSIC-DFA}=E^{DFA}[{\rho }_{\uparrow },{\rho }_{\downarrow }]-\sum _i\{U^{}[{\rho }_{i\sigma }]+E_{XC}^{DFA}[{\rho }_{i\sigma },0]\}.$

This is one-electron self-interaction correction scheme and is exact self-interaction cancellation for one electron cases.

LSIC equation

Reference: https://aip.scitation.org/doi/figure/10.1063/1.5129533

In local SIC method, PZSIC energy densities are scaled down with a local scaling factor or iso-orbital indicator z(r).

$E_{XC}^{LSIC-DFA}=E_{XC}^{DFA}[{\rho }_{\uparrow },{\rho }_{\downarrow }]-\sum _{i,\sigma }^{occ}\{U^{LSIC}[{\rho }_{i,\sigma }]+E_{XC}^{LSIC}[{\rho }_{i,\sigma },0]\}$

where

$U^{LSIC}[{\rho }_{i,\sigma }]=\frac{1}{2}\int d\overrightarrow{r}\{z_{\sigma }(\overrightarrow{r}){\}}^k{\rho }_{i,\sigma }(\overrightarrow{r})\int d\overrightarrow{r^{\prime }}\frac{{\rho }_{i,\sigma }(\overrightarrow{r^{\prime }})}{|\overrightarrow{r}-\overrightarrow{r^{\prime }}|}$

$E_{XC}^{LSIC}[{\rho }_{i,\sigma },0]=\int d\overrightarrow{r}\{z_{\sigma }(\overrightarrow{r}){\}}^k{\rho }_{i,\sigma }(\overrightarrow{r}){ϵ}_{XC}^{DFA}([{\rho }_{i,\sigma },0],\overrightarrow{r}).$

A typical choice for the local scaling factor is

$z(\mathbf{𝐫})=\frac{{\tau }_w(\mathbf{𝐫})}{\tau (\mathbf{𝐫})}$

This quantity becomes unity at the single orbital regions and becomes zero at the uniform density regions. It cannot differentiate weak interaction regions and uniform density region.

Quasi-SCF approach

You can apply the local scaling to PZSIC potentials in place of PZSIC energy densities. This approach is referred as quasi-SCF. The resulting Hamiltonian is as follows,

$H_j=-\frac{1}{2}{\mathrm{\nabla }}^2+v_{ext}(\overrightarrow{r})+\int \frac{\rho (\overrightarrow{r^{\prime }})}{|\overrightarrow{r}-\overrightarrow{r^{\prime }}|}d\overrightarrow{r^{\prime }}+v_{XC}^{DFA}([\rho ],\overrightarrow{r})-f(\overrightarrow{r})(\int \frac{{\rho }_j(\overrightarrow{r^{\prime }})}{|\overrightarrow{r}-\overrightarrow{r^{\prime }}|}d\overrightarrow{r^{\prime }}+v_{XC}^{DFA}([{\rho }_j],\overrightarrow{r}))$

Quasi-SCF approach give better HOMO (closer agreement with NIST IPs) than the original LSIC. But have problems in the spin crossover systems(?).

Gauge problem

With LSIC with PBE or SCAN, XC energy gauge differ from Coulomb gauge.

Successes of LSIC method

Static dipole polarizability

water cluster paper

polyacene paper

Mol pol paper