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Pierre-Francois Loos 2019-11-13 14:22:16 +01:00
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Manuscript/ExPerspective.tex
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@ -84,7 +84,7 @@ We provide a global overview of the successive steps that made possible to obtai
First, we describe the evolution of \textit{ab initio} state-of-the-art methods, with originally Roos' CASPT2 method, and then third-order coupled cluster methods as in the renowned Thiel set of excitation energies described in a remarkable series of papers in the 2000's. First, we describe the evolution of \textit{ab initio} state-of-the-art methods, with originally Roos' CASPT2 method, and then third-order coupled cluster methods as in the renowned Thiel set of excitation energies described in a remarkable series of papers in the 2000's.
More recently, this quest for highly accurate excitation energies was reinitiated thanks to the resurgence of selected configuration interaction (SCI) methods and their efficient parallel implementation. More recently, this quest for highly accurate excitation energies was reinitiated thanks to the resurgence of selected configuration interaction (SCI) methods and their efficient parallel implementation.
These methods have been able to routinely deliver highly accurate excitation energies for small molecules as well as medium-size molecules in compact basis sets for single and double excitations. These methods have been able to routinely deliver highly accurate excitation energies for small molecules as well as medium-size molecules in compact basis sets for single and double excitations.
Second, we describe how these high-level methods and the creation of large, diverse and accurate benchmark sets of excitation energies have allowed to assess fairly and accurately the performances of computationally lighter models (\eg, TD-DFT, BSE, ADC, EOM-CC, etc) for different types of excited states. Second, we describe how these high-level methods and the creation of large, diverse and accurate benchmark sets of excitation energies have allowed to assess fairly and accurately the performances of computationally lighter theoretical models (\eg, TD-DFT, BSE, ADC, EOM-CC, etc) for different types of excited states.
We conclude this \textit{Perspective} by discussing the current potentiality of these methods from both an expert and a non-expert point of view, and what we believe could be the future theoretical and technological developments in the field. We conclude this \textit{Perspective} by discussing the current potentiality of these methods from both an expert and a non-expert point of view, and what we believe could be the future theoretical and technological developments in the field.
\end{abstract} \end{abstract}
@ -320,7 +320,7 @@ These findings were in perfect agreement with our two previous studies. \cite{Lo
This definitely settles down the debate by demonstrating the superiority of CC3 (in terms of accuracy) compared to methods like CCSDT-3 or ADC(3). This definitely settles down the debate by demonstrating the superiority of CC3 (in terms of accuracy) compared to methods like CCSDT-3 or ADC(3).
Moreover, thanks to the exhaustive and detailed comparisons made in Ref.~\onlinecite{Loo20}, we could safely conclude that CC3 also regularly outperforms CASPT2 and NEVPT2 as long as the corresponding transition does not show any strong multiple excitation character. Moreover, thanks to the exhaustive and detailed comparisons made in Ref.~\onlinecite{Loo20}, we could safely conclude that CC3 also regularly outperforms CASPT2 and NEVPT2 as long as the corresponding transition does not show any strong multiple excitation character.
Our current efforts are now focussing on expanding and combining these sets to create an \textit{ultimate} test set of highly-accurate excitations energies. Our current efforts are now focussing on expanding and merging these sets to create an \textit{ultimate} test set of highly-accurate excitations energies.
In particular, we are currently generating reference excitations energies for radicals as well as more ``exotic'' molecules containing heavier atoms (such as \ce{Cl}, \ce{F}, \ce{P}, and \ce{Si}). \cite{Loo20b} In particular, we are currently generating reference excitations energies for radicals as well as more ``exotic'' molecules containing heavier atoms (such as \ce{Cl}, \ce{F}, \ce{P}, and \ce{Si}). \cite{Loo20b}
The combination of these various sets would potentially create a mega-set of more than 400 vertical transition energies for small- and medium-size molecules based on accurate ground-state geometries. The combination of these various sets would potentially create a mega-set of more than 400 vertical transition energies for small- and medium-size molecules based on accurate ground-state geometries.
Such a set would definitely be a terrific asset for the entire electronic structure community. Such a set would definitely be a terrific asset for the entire electronic structure community.