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Pierre-Francois Loos 2021-05-23 14:36:41 +02:00
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%% This BibTeX bibliography file was created using BibDesk. %% This BibTeX bibliography file was created using BibDesk.
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%% Created for Pierre-Francois Loos at 2021-05-23 09:33:22 +0200 %% Created for Pierre-Francois Loos at 2021-05-23 14:27:26 +0200
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@article{Gori-Giorgi_2008,
abstract = {The correlation energy in density functional theory can be expressed exactly in terms of the change in the probability of finding two electrons at a given distance r12 (intracule density) when the electron--electron interaction is multiplied by a real parameter λ varying between 0 (Kohn--Sham system) and 1 (physical system). In this process{,} usually called adiabatic connection{,} the one-electron density is (ideally) kept fixed by a suitable local one-body potential. While an accurate intracule density of the physical system can only be obtained from expensive wavefunction-based calculations{,} being able to construct good models starting from Kohn--Sham ingredients would highly improve the accuracy of density functional calculations. To this purpose{,} we investigate the intracule density in the λ → ∞ limit of the adiabatic connection. This strong-interaction limit of density functional theory turns out to be{,} like the opposite non-interacting Kohn--Sham limit{,} mathematically simple and can be entirely constructed from the knowledge of the one-electron density. We develop here the theoretical framework and{,} using accurate correlated one-electron densities{,} we calculate the intracule densities in the strong interaction limit for few atoms. Comparison of our results with the corresponding Kohn--Sham and physical quantities provides useful hints for building approximate intracule densities along the adiabatic connection of density functional theory.},
author = {Gori-Giorgi, Paola and Seidl, Michael and Savin, Andreas},
date-added = {2021-05-23 14:27:13 +0200},
date-modified = {2021-05-23 14:27:22 +0200},
doi = {10.1039/B803709B},
issue = {23},
journal = {Phys. Chem. Chem. Phys.},
pages = {3440-3446},
title = {Intracule densities in the strong-interaction limit of density functional theory},
volume = {10},
year = {2008},
Bdsk-Url-1 = {http://dx.doi.org/10.1039/B803709B}}
@article{Pearson_2009, @article{Pearson_2009,
author = {Jason K. Pearson and Peter M.W. Gill and Jesus M. Ugalde and Russell J. Boyd}, author = {Jason K. Pearson and Peter M.W. Gill and Jesus M. Ugalde and Russell J. Boyd},
date-added = {2021-05-23 09:33:16 +0200}, date-added = {2021-05-23 09:33:16 +0200},

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@ -57,7 +57,7 @@ Concrete examples are provided in the case of two-electron systems.
\maketitle \maketitle
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\textbf{Uniform electron gases.} \section{Uniform electron gases}
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Alongside the two Hohenberg-Kohn theorems \cite{Hohenberg_1964} which put density-functional theory (DFT) on firm mathematical grounds and the Kohn-Sham (KS) formalism \cite{Kohn_1965} that makes DFT practically feasible, the uniform electron gas (UEG) \cite{Loos_2016} is one of the many pieces of the puzzle that have made DFT \cite{ParrBook} so successful in the past thirty years. Alongside the two Hohenberg-Kohn theorems \cite{Hohenberg_1964} which put density-functional theory (DFT) on firm mathematical grounds and the Kohn-Sham (KS) formalism \cite{Kohn_1965} that makes DFT practically feasible, the uniform electron gas (UEG) \cite{Loos_2016} is one of the many pieces of the puzzle that have made DFT \cite{ParrBook} so successful in the past thirty years.
Indeed, apart from very few exceptions, most density-functional approximations are based, at some level at least, on the UEG via the so-called local-density approximation (LDA) \cite{Thomas_1927,Fermi_1927,Dirac_1930,Slater_1951,Ceperley_1980} which assumes that the electron density $\rho$ of an atom, a molecule, or a solid is locally uniform and has identical ``properties'' to the UEG with the same electron density. Indeed, apart from very few exceptions, most density-functional approximations are based, at some level at least, on the UEG via the so-called local-density approximation (LDA) \cite{Thomas_1927,Fermi_1927,Dirac_1930,Slater_1951,Ceperley_1980} which assumes that the electron density $\rho$ of an atom, a molecule, or a solid is locally uniform and has identical ``properties'' to the UEG with the same electron density.
@ -74,7 +74,7 @@ In the so-called thermodynamic limit where both $n$ and $V$ goes to infinity but
In the following, this paradigm is named the infinite UEG (IUEG) for obvious reasons. In the following, this paradigm is named the infinite UEG (IUEG) for obvious reasons.
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\textbf{Finite uniform electron gases.} \section{Finite uniform electron gases}
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Recently, it has been shown that one can create finite UEGs (FUEGs) by placing a finite number of electrons onto the surface of a sphere of radius $R$. \cite{Tempere_2002,Tempere_2007,Seidl_2007,Loos_2009a,Loos_2009c,Loos_2010e,Loos_2011b,Gill_2012,Loos_2018b} Recently, it has been shown that one can create finite UEGs (FUEGs) by placing a finite number of electrons onto the surface of a sphere of radius $R$. \cite{Tempere_2002,Tempere_2007,Seidl_2007,Loos_2009a,Loos_2009c,Loos_2010e,Loos_2011b,Gill_2012,Loos_2018b}
Of course, FUEGs only appear for well-defined electron numbers and electronic states. \cite{Rogers_2016,Rogers_2017} Of course, FUEGs only appear for well-defined electron numbers and electronic states. \cite{Rogers_2016,Rogers_2017}
@ -148,7 +148,7 @@ For the other electronic states corresponding to higher total angular momentum,
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\textbf{Transient uniform electron gases.} \section{Transient uniform electron gases}
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As evidenced by Eq.~\eqref{eq:rho}, both the angular and interelectronic wave functions contribute to the electron density and a subtle interplay between these two quantities may result in a uniform density. As evidenced by Eq.~\eqref{eq:rho}, both the angular and interelectronic wave functions contribute to the electron density and a subtle interplay between these two quantities may result in a uniform density.
To illustrate this, let us consider explicit examples. To illustrate this, let us consider explicit examples.
@ -218,11 +218,11 @@ Actually, it is even possible for a system to be a TUEG within the exact treatme
Expanding the two HF orbitals of the $^3P$ ground state in a basis of zonal harmonics $Y_{\ell}(\theta) \equiv Y_{\ell 0}(\theta,\phi)$, we have not found any $R$ values for which the HF electron density, $\rho^\text{HF}(\theta)$, is uniform. Expanding the two HF orbitals of the $^3P$ ground state in a basis of zonal harmonics $Y_{\ell}(\theta) \equiv Y_{\ell 0}(\theta,\phi)$, we have not found any $R$ values for which the HF electron density, $\rho^\text{HF}(\theta)$, is uniform.
However, at $R \approx \SI{-7}{\bohr}$, $\rho^\text{HF}$ is \textit{locally} uniform around $\theta = \pi/2$ (\ie, in the $xy$ plane), as shown in Fig.~\ref{fig:HF}. However, at $R \approx \SI{-7}{\bohr}$, $\rho^\text{HF}$ is \textit{locally} uniform around $\theta = \pi/2$ (\ie, in the $xy$ plane), as shown in Fig.~\ref{fig:HF}.
We believe that this outcome is a direct consequence of the single-determinant nature of the HF approximation which can only include, by definition, one of the three equivalent $sp$ configurations (\ie, $sp_x$, $sp_y$, and $sp_z$). We believe that this outcome is a direct consequence of the single-determinant nature of the HF approximation which can only include, by definition, one of the three equivalent $sp$ configurations (\ie, $sp_x$, $sp_y$, and $sp_z$).
The fact that this phenomenon appears at larger (absolute) $R$ values in the HF approximation is not surprising as, contrary to the repulsive regime (\ie, $R > 0$) where the electrons are too close to each other at the HF level (compared to the exact picture), \cite{Pearson_2009} in the attractive regime (\ie, $R < 0$) they are too far away from each other. The fact that this phenomenon appears at larger (absolute) $R$ values in the HF approximation is not surprising as, contrary to the repulsive regime (\ie, $R > 0$) where the electrons are too close to each other at the HF level (compared to the exact picture), \cite{Gori-Giorgi_2008,Pearson_2009} in the attractive regime (\ie, $R < 0$) they are too far away from each other.
This implies that the interaction strength has to be greater (which is equivalent to a larger absolute $R$ value) to overcome this drawback. \cite{Seidl_2010,Burton_2019a,Marie_2020} This implies that the interaction strength has to be greater (which is equivalent to a larger absolute value of $R$) to overcome this drawback. \cite{Seidl_2010,Burton_2019a,Marie_2020}
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\textbf{Concluding remarks.} \section{Concluding remarks}
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Here, we have introduced the concept of transient UEGs (TUEGs), a novel family of electron gases that exhibit, in very particular conditions, homogenous densities. Here, we have introduced the concept of transient UEGs (TUEGs), a novel family of electron gases that exhibit, in very particular conditions, homogenous densities.
Using the electrons-on-a-sphere model, we have presented an example of such TUEGs created thanks to the competing effects of the Pauli exclusion principle and the creation of an attractive electron pair. Using the electrons-on-a-sphere model, we have presented an example of such TUEGs created thanks to the competing effects of the Pauli exclusion principle and the creation of an attractive electron pair.
@ -231,11 +231,13 @@ As a final remark, we would like to mention that a very similar analysis can be
The three-dimensional version where electrons are confined to the surface of a 3-sphere (or glome) could be of particular interest, especially in the context of the development of new exchange-correlation functionals within DFT.\cite{Sun_2015,Agboola_2015,Loos_2017a} The three-dimensional version where electrons are confined to the surface of a 3-sphere (or glome) could be of particular interest, especially in the context of the development of new exchange-correlation functionals within DFT.\cite{Sun_2015,Agboola_2015,Loos_2017a}
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\textbf{Acknowledgements.} \section*{Acknowledgements}
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This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant agreement No.~863481). This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant agreement No.~863481).
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\section*{References}
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\bibliography{TrUEGs} \bibliography{TrUEGs}
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