diff --git a/Manuscript/rsdft-cipsi-qmc.tex b/Manuscript/rsdft-cipsi-qmc.tex index 84797a5..156fc57 100644 --- a/Manuscript/rsdft-cipsi-qmc.tex +++ b/Manuscript/rsdft-cipsi-qmc.tex @@ -1143,7 +1143,7 @@ The context is rather different within KS-DFT. Indeed, mainstream density functionals have distinct functional forms to take into account correlation effects of same-spin and opposite-spin electron pairs. Therefore, KS determinants corresponding to different values of $m_s$ lead to different total energies. -Consequently, in the context of RS-DFT, the determinant expansions is impacted by this spurious effect, as opposed to FCI. +Consequently, in the context of RS-DFT, the determinant expansion is impacted by this spurious effect, as opposed to FCI. In this Appendix, we investigate the impact of the spin contamination on the FN-DMC energy originating from the short-range density functional. We have @@ -1162,7 +1162,12 @@ $2$ m\hartree{}, is obtained for $\mu=0$, but this bias decreases quickly below $1$ m\hartree{} when $\mu$ increases. As expected, with $\mu=\infty$ we observe a perfect spin-invariance of the energy (within the error bars), and the bias is not noticeable for $\mu=5$~bohr$^{-1}$. -\titou{T2: what do you conclude from this section? What value of $m_s$ do you use to compute the atoms?} + +Hence, at the FN-DMC level the error due to the lack of +spin-invariance with RS-DFT-CIPSI trial wave functions is below the +chemical accuracy, and is not expected to be problematic for the +comparison of energies of systems with different spin quantum numbers +as in atomization energies. %%% TABLE IV %%% \begin{table}