This method is based on density embedding. Let's introduce first the subtraction scheme definition of the density embedding method:

$\displaystyle E_{tot} = E_{HK}[\rho_{tot}] - \sum_{A}E_{HK}[\rho_{A}] + \sum_{A}E_{KS}[\rho_{A}]$.

The total electronic density of the $\rho_{tot} = \sum_{A}\rho_{A}$ as the sum over all the subsystems $A$ of the subsystem densities $\rho_{A}$. The energy functionals $E_{HK}$ and $E_{KS}$ are the Hohenberg–Kohn and the Kohn–Sham functionals, respectively.

$\displaystyle E_{HK}[\rho] = T_{HK}[\rho] + E_{ext}^{HK}[\rho] + \frac{1}{2} \int\int \frac{\rho(r)\rho(r')}{r-r'}drdr' + E_{XC}[\rho]$.
$\displaystyle E_{KS}[P] = T_{S}[P] + E_{ext}[P] + \frac{1}{2} \int\int \frac{\rho(r)\rho(r')}{r-r'}drdr' + E_{XC}[\rho]$.

where $P$ is the reduced one-particle density matrix of the system. In order to arrive at the working equations, one has to introduce the restriction that the external energy functional in the Hohenberg–Kohn energy is linear in the density.

$\displaystyle E_{ext}^{HK}[\rho_{tot}] = \sum_{A}E_{ext}^{HK}[\rho_{A}]$.

Now, if one calls the classical Coulomb term $E_{hxc}[\rho]$ and defines the non-additive kinetic energy as $T_{nadd}[\rho,{\rho_{A}}] = T_{HK}[\rho]−\sum_{A}T_{HK}[\rho_{A}]$, the obtained working equation would be:

$\displaystyle E_{tot}[{P_{A}}] =\sum_{A}(T_{S}[P_{A}] + E_{ext}[P_{A}]) + E_{hxc}[\rho] + T_{nadd}[{P_{A}}]$.

To avoid the integration of the kinetic energy functional for each subsystem, an atomic potential approximation can be applied. For a local potential one can write:

$\displaystyle T_{nadd} = T_{S}[\rho]−\sum_{A}T_{S}[\rho_{A}] =$
$\displaystyle \int\rho\mu[\rho]dr - \sum_{a}\int\rho_{A}\mu[\rho_{A}]dr =$
$\displaystyle \sum_{a}\int\rho_{A}(\mu[\rho]-\mu[\rho_{A}])dr$

Making a linearization approximation for the functional $\mu[\rho]$

$\displaystyle \mu[\rho]-\mu[\rho_{A}] \sim \sum_{B/not = A} \frac{\partial \mu[\rho_{A}]}{\partial \rho} \rho_{B} = \mu'[\rho_{A}]$
$\displaystyle T_{nadd} = \sum_{A}T_{S}\sum_{B/not = A}\int\mu'[\rho_{A}]\rho_{A}\rho_{B}dr$

A further approximation of the derivative functional in atomic contributions is:

$\displaystyle \mu'[\rho_{A}]\rho_{A} = V^{K}[\rho_{A}] \sim \sum_{a \in A}V_{a}^{K}(R_{a})$

and the realization that a typical kinetic energy functional is proportional to $\rho^{5/3}$ leads to a model for the final atomic local potential of the form:

$\displaystyle V_{a}^{K}(R_{a}) = N_{a}\rho_{a}^{2/3}$

where $\rho_{a}$ is a model atomic density. Such local potential can help to speed up the underlying embedding calculation.

First of all, one has to choose the TNADD_METHOD. For the first type of calculation, discussed in the previous section, the keyword to select is EMBEDDING (default). Inside the KG_METHOD the XC functional can be selected:

    &XC
      &XC_FUNCTIONAL
        &KE_GGA
          FUNCTIONAL T92
        &END
      &END
    &END