Density-functional approximation for the correlation energy of the inhomogeneous electron gas

1986 ◽  
Vol 33 (12) ◽  
pp. 8822-8824 ◽  
Author(s):  
John P. Perdew
Keyword(s):  
Density Functional ◽  
Correlation Energy ◽  
Electron Gas ◽  
Functional Approximation

scholarly journals Approximate bounds and temperature dependence of adiabatic connection integrands for the uniform electron gas

2021 ◽  
Author(s):  
Brittany P. Harding ◽  
Zachary Mauri ◽  
Aurora Pribram-Jones
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Correlation Energy ◽  
Electron Gas ◽  
High Energy ◽  
Zero Temperature ◽  
Temperature Dependent ◽  
Functional Theory ◽  
Exchange Correlation ◽  
Uniform Electron Gas

Thermal density functional theory is commonly used in simulations of warm dense matter, a highly energetic phase characterized by substantial thermal effects and by correlated electrons demanding quantum mechanical treatment. The numerous approximations for the exchange-correlation energy component in zero-temperature density functional theory, though often used in these high-energy-density simulations with Fermi-weighted electronic densities, are known to miss temperature-dependent effects in the electronic structure of these systems. In this work, the temperature-dependent adiabatic connection is demonstrated and analyzed using a well-known parameterization of the uniform electron gas free energy. Useful tools based on this formalism for analyzing and constraining approximations of the exchange-correlation at zero temperature are leveraged for the finite-temperature case. Inspired by the Lieb-Oxford inequality, which provides a lower bound for the ground-state exchange-correlation energy, bounds for the exchange-correlation at finite-temperatures are approximated for various degrees of electronic correlation.

scholarly journals Approximate bounds and temperature dependence of adiabatic connection integrands for the uniform electron gas

2021 ◽  
Author(s):  
Brittany P. Harding ◽  
Zachary Mauri ◽  
Aurora Pribram-Jones
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Correlation Energy ◽  
Electron Gas ◽  
High Energy ◽  
Zero Temperature ◽  
Temperature Dependent ◽  
Functional Theory ◽  
Exchange Correlation ◽  
Uniform Electron Gas

Thermal density functional theory is commonly used in simulations of warm dense matter, a highly energetic phase characterized by substantial thermal effects and by correlated electrons demanding quantum mechanical treatment. The numerous approximations for the exchange-correlation energy component in zero-temperature density functional theory, though often used in these high-energy-density simulations with Fermi-weighted electronic densities, are known to miss temperature-dependent effects in the electronic structure of these systems. In this work, the temperature-dependent adiabatic connection is demonstrated and analyzed using a well-known parameterization of the uniform electron gas free energy. Useful tools based on this formalism for analyzing and constraining approximations of the exchange-correlation at zero temperature are leveraged for the finite-temperature case. Inspired by the Lieb-Oxford inequality, which provides a lower bound for the ground-state exchange-correlation energy, bounds for the exchange-correlation at finite temperatures are approximated for various degrees of electronic correlation.

scholarly journals CORRELATION ENERGY OF AN ELECTRON GAS: A FUNCTIONAL APPROACH

2003 ◽  
Vol 17 (07) ◽  
pp. 973-1009 ◽  
Author(s):  
A. REBEI ◽  
W. N. G. HITCHON
Keyword(s):  
Effective Action ◽  
Density Functional ◽  
Correlation Energy ◽  
Random Phase ◽  
Electron Gas ◽  
Density Functional Method ◽  
Functional Method ◽  
Correlation Effects ◽  
Action Functional ◽  
Point Correlation

Correlation effects of an electron gas in an external potential are derived using an Effective Action functional method. Corrections beyond the random phase approximation (RPA) are naturally incorporated by this method. The Effective Action functional is made to depend explicitly on two-point correlation functions. The calculation is carried out at imaginary time. For a homogeneous electron gas, we calculate the effect of exchange on the ring diagrams at zero temperature and show how to include some of the ladder diagrams. Our results agree well with known numerical calculations. We conclude by showing that this method is in fact a variant of the time dependent density functional method and suggest that it is suitable to be applied to the study of correlation effects in the non-homogeneous case.

Exchange-Correlation Energy Densities and Response Potentials: Connection Between Two Definitions and Analytical Model for the Strong-Coupling Limit of a Stretched Bond

2019 ◽  
Author(s):  
S. Giarrusso ◽  
Paola Gori-Giorgi
Keyword(s):  
Density Functional Theory ◽  
Strong Coupling ◽  
Density Functional ◽  
Correlation Energy ◽  
Order Term ◽  
Strong Coupling Limit ◽  
Local Form ◽  
Coupling Constant ◽  
Functional Theory ◽  
Exchange Correlation

We analyze in depth two widely used definitions (from the theory of conditional probablity amplitudes and from the adiabatic connection formalism) of the exchange-correlation energy density and of the response potential of Kohn-Sham density functional theory. We introduce a local form of the coupling-constant-dependent Hohenberg-Kohn functional, showing that the difference between the two definitions is due to a corresponding local first-order term in the coupling constant, which disappears globally (when integrated over all space), but not locally. We also design an analytic representation for the response potential in the strong-coupling limit of density functional theory for a model single stretched bond.<br>

Electronic Structure Benchmark Calculations of Inorganic and Biochemical Carboxylation Reactions

2018 ◽  
Author(s):  
Oscar A. Douglas-Gallardo ◽  
David A. Sáez ◽  
Stefan Vogt-Geisse ◽  
Esteban Vöhringer-Martinez
Keyword(s):  
Electronic Structure ◽  
Chemical Reactions ◽  
Density Functional ◽  
Correlation Energy ◽  
Electronic Energy ◽  
Basis Sets ◽  
Electronic Correlation ◽  
Correct Description ◽  
Carbon Dioxide Co2 ◽  
High Level

<div><div><div><p>Carboxylation reactions represent a very special class of chemical reactions that is characterized by the presence of a carbon dioxide (CO2) molecule as reactive species within its global chemical equation. These reactions work as fundamental gear to accomplish the CO2 fixation and thus to build up more complex molecules through different technological and biochemical processes. In this context, a correct description of the CO2 electronic structure turns out to be crucial to study the chemical and electronic properties associated with this kind of reactions. Here, a sys- tematic study of CO2 electronic structure and its contribution to different carboxylation reaction electronic energies has been carried out by means of several high-level ab-initio post-Hartree Fock (post-HF) and Density Functional Theory (DFT) calculations for a set of biochemistry and inorganic systems. We have found that for a correct description of the CO2 electronic correlation energy it is necessary to include post-CCSD(T) contributions (beyond the gold standard). These high-order excitations are required to properly describe the interactions of the four π-electrons as- sociated with the two degenerated π-molecular orbitals of the CO2 molecule. Likewise, our results show that in some reactions it is possible to obtain accurate reaction electronic energy values with computationally less demanding methods when the error in the electronic correlation energy com- pensates between reactants and products. Furthermore, the provided post-HF reference values allowed to validate different DFT exchange-correlation functionals combined with different basis sets for chemical reactions that are relevant in biochemical CO2 fixing enzymes.</p></div></div></div>

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