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1. Wavelength‐decomposition‐based embedded cluster density approximation for systems with nonlocal electron correlation

   https://doi.org/10.1002/qua.26347  

   Huang, Chen ( July 2020 , International Journal of Quantum Chemistry)

   Local correlation methods rely on the assumption that electron correlation is nearsighted. In this work, we develop a method to alleviate this assumption. This new method is demonstrated by calculating the random phase approximation (RPA) correlation energies in several one‐dimensional model systems. In this new method, the first step is to approximately decompose the RPA correlation energy to the nearsighted and farsighted components based on the wavelength decomposition of electron correlation developed by Langreth and Perdew. The short‐wavelength (SW) component of the RPA correlation energy is then considered to be nearsighted, and the long‐wavelength (LW) component of the RPA correlation energy is considered to be farsighted. The SW RPA correlation energy is calculated using a recently developed local correlation method: the embedded cluster density approximation (ECDA). The LW RPA correlation energy is calculated globally based on the system's Kohn‐Sham orbitals. This new method is termedλ‐ECDA, whereλindicates the wavelength decomposition. The performance ofλ‐ECDA is examined on a one‐dimensional model system: aH₂₄chain, in which the RPA correlation energy is highly nonlocal. In this model system, a softened Coulomb interaction is used to describe the electron‐electron and electron‐ion interactions, and slightly stronger nuclear charges (1.2e) are assigned to the pseudo‐H atoms. Bond stretching energies, RPA correlation potentials, and Kohn‐Sham eigenvalues predicted byλ‐ECDA are in good agreement with the benchmarks when the clusters are made reasonably large. We find that the LW RPA correlation energy is critical for obtaining accurate prediction of the RPA correlation potential, even though the LW RPA correlation energy contributes to only a few percent of the total RPA correlation energy.

    

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2. Multiconfiguration Pair-Density Functional Theory

   Prachi Sharma, Jie J. ( April 2021 , Annual review of physical chemistry)

   Kohn-Sham density functional theory with the available exchange–correlation functionals is less accurate for strongly correlated systems, which require a multiconfigurational description as a zero-order function, than for weakly correlated systems, and available functionals of the spin densities do not accurately predict energies for many strongly correlated systems when one uses multiconfigurational wave functions with spin symmetry. Furthermore, adding a correlation functional to a multiconfigurational reference energy can lead to double counting of electron correlation. Multiconfiguration pair-density functional theory (MC-PDFT) overcomes both obstacles, the second by calculating the quantum mechanical part of the electronic energy entirely by a functional, and the first by using a functional of the total density and the on-top pair density rather than the spin densities. This allows one to calculate the energy of strongly correlated systems efficiently with a pair-density functional and a suitable multiconfigurational reference function. This article reviews MC-PDFT and related background information. 

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3. Beyond the RPA and GW methods with adiabatic xc-kernels for accurate ground state and quasiparticle energies

   https://doi.org/10.1038/s41524-019-0242-8  

   Olsen, Thomas ; Patrick, Christopher E. ; Bates, Jefferson E. ; Ruzsinszky, Adrienn ; Thygesen, Kristian S. ( November 2019 , npj Computational Materials)

   We review the theory and application of adiabatic exchange–correlation (xc)-kernels for ab initio calculations of ground state energies and quasiparticle excitations within the frameworks of the adiabatic connection fluctuation dissipation theorem and Hedin’s equations, respectively. Various different xc-kernels, which are all rooted in the homogeneous electron gas, are introduced but hereafter we focus on the specific class of renormalized adiabatic kernels, in particular the rALDA and rAPBE. The kernels drastically improve the description of short-range correlations as compared to the random phase approximation (RPA), resulting in significantly better correlation energies. This effect greatly reduces the reliance on error cancellations, which is essential in RPA, and systematically improves covalent bond energies while preserving the good performance of the RPA for dispersive interactions. For quasiparticle energies, the xc-kernels account for vertex corrections that are missing in the GW self-energy. In this context, we show that the short-range correlations mainly correct the absolute band positions while the band gap is less affected in agreement with the known good performance of GW for the latter. The renormalized xc-kernels offer a rigorous extension of the RPA and GW methods with clear improvements in terms of accuracy at little extra computational cost.

    

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4. An exact method for bosonizing the Fermi surface in arbitrary dimensions

   https://doi.org/10.21468/SciPostPhys.16.3.069  

   Park, Takamori ; Balents, Leon ( January 2024 , SciPost Physics)

   Inspired by the recent work by Delacretaz et. al. [Phys. Rev. Res. 4, 033131 (2022)], we rigorously derive an exact and simple method to bosonize a non-interacting fermionic system with a Fermi surface starting from a microscopic Hamiltonian. In the long-wavelength limit, we show that the derived bosonized action is exactly equivalent to the action obtained by Delacretaz et. al. In addition, we propose diagrammatic rules to evaluate correlation functions using our bosonized theory and demonstrate these rules by calculating the three- and four-point density correlation functions. We also consider a general density-density interaction and show that the simplest approximation in our bosonic theory is identical to RPA results.

    

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5. Strong electron correlation from partition density functional theory

   https://doi.org/10.1063/5.0175538  

   Shi, Yi ; Shi, Yuming ; Wasserman, Adam ( December 2023 , The Journal of Chemical Physics)

   Standard approximations for the exchange–correlation functional in Kohn–Sham density functional theory (KS-DFT) typically lead to unacceptably large errors when applied to strongly correlated electronic systems. Partition-DFT (PDFT) is a formally exact reformulation of KS-DFT in which the ground-state density and energy of a system are obtained through self-consistent calculations on isolated fragments, with a partition energy representing inter-fragment interactions. Here, we show how typical errors of the local density approximation (LDA) in KS-DFT can be largely suppressed through a simple approximation, the multi-fragment overlap approximation (MFOA), for the partition energy in PDFT. Our method is illustrated on simple models of one-dimensional strongly correlated linear hydrogen chains. The MFOA, when used in combination with the LDA for the fragments, improves LDA dissociation curves of hydrogen chains and produces results that are comparable to those of spin-unrestricted LDA, but without breaking the spin symmetry. MFOA also induces a correction to the LDA electron density that partially captures the correct density dimerization in strongly correlated hydrogen chains. Moreover, with an additional correction to the partition energy that is specific to the one-dimensional LDA, the approximation is shown to produce dissociation energies in quantitative agreement with calculations based on the density matrix renormalization group method.

    

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