diff --git a/Manuscript/SI/srDFT_SC-SI.tex b/Manuscript/SI/srDFT_SC-SI.tex index a4d0d87..5c9ab54 100644 --- a/Manuscript/SI/srDFT_SC-SI.tex +++ b/Manuscript/SI/srDFT_SC-SI.tex @@ -286,16 +286,16 @@ \section{Size consistency of the basis-set correction} -\subsection{General considerations} +\subsection{Sufficient condition for size consistency} -The following paragraph gives a proof of the size consistency of the basis-set correction. The basis-set correction is expressed as an integral in real space +The basis-set correction is expressed as an integral in real space \begin{equation} \label{eq:def_ecmdpbebasis} \begin{aligned} & \efuncdenpbe{\argebasis} = \\ & \int \text{d}\br{} \,\denr \ecmd(\argrebasis), \end{aligned} \end{equation} -where all the local quantities $\argrebasis$ are obtained from the same wave function $\Psi$. In the limit of two dissociated fragments $\text{A}+\text{B}$, this integral can be rewritten as the sum of the integral over the region $\Omega_\text{A}$ and the integral over the region $\Omega_\text{B}$ +where all the local quantities $\argrebasis$ are obtained from the same wave function $\Psi$. In the limit of two non-overlapping and non-interacting dissociated fragments $\text{A}+\text{B}$, this integral can be rewritten as the sum of the integral over the region $\Omega_\text{A}$ and the integral over the region $\Omega_\text{B}$ \begin{equation} \label{eq:def_ecmdpbebasis} \begin{aligned} @@ -329,25 +329,13 @@ where the left-hand-side quantities are for the supersystem and the right-hand-s \begin{equation} \ket{\wf{\text{A}+\text{B}}{}} = \ket{\wf{\text{A}}{}} \otimes \ket{\wf{\text{B}}{}}, \end{equation} -where $\otimes$ is the antisymmetric tensor product. In this case, it is well known that Eqs.~(\ref{nAB})-(\ref{sAB}) are valid and it remains to show that Eqs.~(\ref{n2AB}) and~(\ref{muAB}) are also valid. +where $\otimes$ is the antisymmetric tensor product. In this case, it is easy to shown that Eqs.~(\ref{nAB})-(\ref{sAB}) are valid, as well known, and it remains to show that Eqs.~(\ref{n2AB}) and~(\ref{muAB}) are also valid. Before showing this, we note that even though we do not explicity consider the case of degeneracies, the lack of size consistency which could arise from spin-multiplet degeneracies can be avoided by the same strategy used for imposing the energy independence on $S_z$, i.e. by using the effective spin polarization $\tilde{\zeta}(n(\br{}),n_{2}(\br{}))$ or a zero spin polarization $\zeta(\br{}) = 0$. Moreover, the lack of size consistency which could arise from spatial degeneracies (e.g., coming from atomic p states) can also be avoided by selecting the same member of the ensemble in the supersystem and in the isolated fragement. This applies to the systems treated in this work. -For spatial degeneracies such as different p states, by selected the same member of the ensemble in the supersystem and the isolated fragements. - -applies to the systems treated in this work. - -Even though this does deal with the case of degeneracies, - -To avoid difficulties arising from spin-multiplet degeneracy, we can use the effective spin polarization $\tilde{\zeta}(n(\br{}),n_{2}(\br{}))$ depending only on $n(\br{})$ and $n_{2}(\br{})$ or a zero spin polarization $\zeta(\br{}) = 0$. - - -Regarding the density and its gradients, these are necessary intensive quantities. The remaining questions are therefore the local range-separation parameter $\murpsi$ and the on-top pair density. - - -\subsection{Property of the on-top pair density} +\subsection{Intensivity of the on-top pair density} A crucial ingredient in the type of functionals used in the present paper together with the definition of the local-range separation parameter is the on-top pair density defined as \begin{equation} \label{eq:def_n2} - n_{2,\wf{}{}}(\br{}) = \sum_{pqrs} \SO{p}{} \SO{q}{} \Gam{pq}{rs} \SO{r}{} \SO{s}{}, + n_{2{}}(\br{}) = \sum_{pqrs} \SO{p}{} \SO{q}{} \Gam{pq}{rs} \SO{r}{} \SO{s}{}, \end{equation} with $\Gam{pq}{rs} = 2 \mel*{\wf{}{}}{ \aic{r_\downarrow}\aic{s_\uparrow}\ai{q_\uparrow}\ai{p_\downarrow}}{\wf{}{}}$. Assume now that the wave function $\wf{A+B}{}$ of the super system $A+B$ can be written as a product of two wave functions defined on two non-overlapping and non-interacting fragments $A$ and $B$