T2 done

Manuscript/Ex-srDFT.bib

@@ -1,13 +1,37 @@
 %% This BibTeX bibliography file was created using BibDesk.
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-%% Created for Pierre-Francois Loos at 2019-07-01 12:03:08 +0200 
+%% Created for Pierre-Francois Loos at 2019-07-01 14:00:38 +0200 
 
 
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+@article{LooGalJac-JPCL-18,
+	Author = {Loos, Pierre-Fran{\c c}ois and Galland, Nicolas and Jacquemin, Denis},
+	Date-Added = {2019-07-01 13:58:30 +0200},
+	Date-Modified = {2019-07-01 13:59:12 +0200},
+	Doi = {10.1021/acs.jpclett.8b02058},
+	Journal = {J. Phys. Chem. Lett.},
+	Number = {16},
+	Pages = {4646--4651},
+	Title = {Theoretical 0--0 Energies with Chemical Accuracy},
+	Volume = {9},
+	Year = {2018},
+	Bdsk-Url-1 = {https://doi.org/10.1021/acs.jpclett.8b02058}}
+
+@article{LooJac-JCTC-19,
+	Author = {P. F. Loos and D. Jacquemin},
+	Date-Added = {2019-07-01 13:57:45 +0200},
+	Date-Modified = {2019-07-01 14:00:29 +0200},
+	Doi = {10.1021/acs.jctc.8b01103},
+	Journal = {J. Chem. Theory Comput.},
+	Pages = {2481--2491},
+	Title = {Chemically accurate 0-0 energies with not-so-accurate excited state geometries},
+	Volume = {15},
+	Year = {2019}}
+
 @article{LooGil-MP-10,
 	Author = {P. F. Loos and P. M. W. Gill},
 	Date-Added = {2019-07-01 09:27:40 +0200},

Manuscript/Ex-srDFT.tex

@@ -176,7 +176,7 @@
 \affiliation{\LCPQ}
 
 \begin{abstract}
-By combining extrapolated selected configuration interaction (sCI) energies obtained with the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) algorithm with the recently proposed short-range density-functional correction for basis-set incompleteness [\href{https://doi.org/10.1063/1.5052714}{Giner \textit{et al.}, \textit{J.~Chem.~Phys.}~\textbf{149}, 194301 (2018)}], we show that one can get chemically accurate vertical and adiabatic excitation energies with, typically, augmented double-$\zeta$ basis sets.
+By combining extrapolated selected configuration interaction (sCI) energies obtained with the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) algorithm with the recently proposed short-range density-functional correction for basis-set incompleteness [\href{https://doi.org/10.1063/1.5052714}{Giner \textit{et al.}, \textit{J.~Chem.~Phys.}~ \textbf{2018}, \textit{149}, 194301}], we show that one can get chemically accurate vertical and adiabatic excitation energies with, typically, augmented double-$\zeta$ basis sets.
 We illustrate the present approach on various types of excited states (valence, Rydberg, and double excitations) in several small organic molecules (methylene, water, ammonia, carbon dimer and ethylene).
 The present study clearly evidences that special care has to be taken with very diffuse excited states where the present correction does not catch the radial incompleteness of the one-electron basis set.
 \end{abstract}
@@ -443,10 +443,12 @@ We have also computed total energies at the exFCI/AV5Z level and used these alon
 \begin{equation}
 	\E{}{\text{AVXZ}}(\tX) = \E{}{\CBS} + \frac{\alpha}{\tX^{3}}.
 \end{equation}
-
 These results are illustrated in Fig.~\ref{fig:CH2} and reported in Table \ref{tab:CH2} alongside reference values from the literature obtained with various deterministic and stochastic approaches. \cite{ChiHolAdaOttUmrShaZim-JPCA-18, SheLeiVanSch-JCP-98, JenBun-JCP-88, SheLeiVanSch-JCP-98, ZimTouZhaMusUmr-JCP-09}
 Total energies for each state can be found in the {\SI}.
-\titou{Comment on the difference between DMC and CBS results.}
+The exFCI/CBS values are still off by a few tenths of a {\kcal} compared to the DMC results of Zimmerman et al. \cite{ZimTouZhaMusUmr-JCP-09} which are extremely close from the experimentally-derived adiabatic energies.
+The reason of this discrepancy is probably due to the frozen-core approximation which has been applied in our case and has shown to significantly affect adiabatic energies. \cite{LooGalJac-JPCL-18, LooJac-JCTC-19}
+However, the exFCI/CBS energies are in perfect agreement with the semistochastic heat-bath CI (SHCI) calculations from Ref.~\onlinecite{ChiHolAdaOttUmrShaZim-JPCA-18}, as expected.
+
 Figure \ref{fig:CH2} clearly shows that, for the double-$\zeta$ basis, the exFCI adiabatic energies are far from being chemically accurate with errors as high as 0.15 eV.
 From the triple-$\zeta$ basis onward, the exFCI excitation energies are chemically accurate though (i.e. error below 1 {\kcal} or 0.043 eV), and converge steadily to the CBS limit when one increases the size of the basis set.
 Concerning the basis-set correction, already at the double-$\zeta$ level, the $\PBEot$ correction returns chemically accurate excitation energies.
@@ -806,9 +808,7 @@ As a final example, we consider the ethylene molecule, yet another system which
 We refer the interested reader to the work of Feller \textit{et al.}\cite{FelPetDav-JCP-14} for an exhaustive investigation dedicated to the excited states of ethylene using state-of-the-art CI calculations.
 In the present context, ethylene is a particularly interesting system as it contains a mixture of valence and Rydberg excited states. 
 Our basis-set corrected vertical excitation energies are gathered in Table \ref{tab:Mol} and depicted in Fig.~\ref{fig:C2H4}.
-%Except for one particular excitation (the lowest singlet-triplet excitation $1\,^{1}A_{1g} \ra 1\,^{3}B_{1u}$), 
 The exFCI+$\PBEot$/AVDZ excitation energies are at near chemical accuracy and the errors drop further when one goes to the triple-$\zeta$ basis.
-%(Note that one cannot afford exFCI/AVQZ calculations for ethylene.)
 Consistently with the previous examples, the $\LDA$ and $\PBEUEG$ functionals are slightly less accurate, although they still correct the excitation energies in the right direction.
 
 %%% FIG 6 %%%
@@ -839,7 +839,7 @@ See {\SI} for geometries and additional information (including total energies an
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 \begin{acknowledgements}
 PFL would like to thank Denis Jacquemin for numerous discussions on excited states.
-This work was performed using HPC resources from GENCI-TGCC (Grant No.~2018-A0040801738), CALMIP (Toulouse) under allocation 2019-18005 and the Obelix cluster from the \textit{Institut Parisien de Chimie Physique et Th\'eorique}.
+This work was performed using HPC resources from GENCI-TGCC (Grant No.~2018-A0040801738), CALMIP (Toulouse) under allocation 2019-18005 and the Ob\'elix cluster from the \textit{Institut Parisien de Chimie Physique et Th\'eorique}.
 \end{acknowledgements}
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