Enhancing Density Functional Theory for Static Correlation in Large Molecules

• URL: http://arxiv.org/abs/2411.02254v1
• Date: Mon, 04 Nov 2024 16:43:32 GMT
• Title: Enhancing Density Functional Theory for Static Correlation in Large Molecules
• Authors: Daniel Gibney, Jan-Niklas Boyn, David A. Mazziotti,
• Abstract summary: A critical challenge for density functional theory (DFT) in practice is its limited ability to treat static electron correlation. Recently, we combined one- and two-electron reduced density matrix theories with DFT to obtain a universal $O(N3)$ generalization of DFT for static correlation. We apply the resulting functional theory to linear hydrogen chains as well as the prediction of the singlet-triplet gap and equilibrium geometries of acenes.
• Score: 0.0
• License:
• Abstract: A critical challenge for density functional theory (DFT) in practice is its limited ability to treat static electron correlation, leading to errors in its prediction of charges, multiradicals, and reaction barriers. Recently, we combined one- and two-electron reduced density matrix theories with DFT to obtain a universal $O(N^3)$ generalization of DFT for static correlation. In this Letter, we enhance the theory's treatment of large molecules by renormalizing the trace of the two-electron identity matrix in the correction using Cauchy-Schwarz inequalities of the electron-electron repulsion matrix. We apply the resulting functional theory to linear hydrogen chains as well as the prediction of the singlet-triplet gap and equilibrium geometries of a series of acenes. This renormalization of the generalized DFT retains the $O(N^{3})$ computational scaling of DFT while enabling the accurate treatment of static correlation for a broad range of molecules and materials.

Related papers

• Quantum phase transitions in one-dimensional nanostructures: a comparison between DFT and DMRG methodologies [0.0]
  We use Density Functional Theory and Density Matrix Renormalization Group to address electronic correlation effects in diverse molecular systems. For the confined chains, DFT performs better for metallic phases, while the highest deviations appear for the Mott and band-insulator phases.
  arXiv  Detail & Related papers  (2024-02-19T19:10:00Z)
• Fourier Neural Differential Equations for learning Quantum Field Theories [57.11316818360655]
  A Quantum Field Theory is defined by its interaction Hamiltonian, and linked to experimental data by the scattering matrix. In this paper, NDE models are used to learn theory, Scalar-Yukawa theory and Scalar Quantum Electrodynamics. The interaction Hamiltonian of a theory can be extracted from network parameters.
  arXiv  Detail & Related papers  (2023-11-28T22:11:15Z)
• Orbital-Free Density Functional Theory with Continuous Normalizing Flows [54.710176363763296]
  Orbital-free density functional theory (OF-DFT) provides an alternative approach for calculating the molecular electronic energy. Our model successfully replicates the electronic density for a diverse range of chemical systems.
  arXiv  Detail & Related papers  (2023-11-22T16:42:59Z)
• Comparison of Density-Matrix Corrections to Density Functional Theory [0.0]
  Density functional theory (DFT) fails to describe systems with statically correlated electrons. We transform DFT into a one-electron reduced density matrix theory (1-RDMFT) We generalize the information density matrix functional theory (iDMFT)
  arXiv  Detail & Related papers  (2022-12-29T16:50:16Z)
• Simulating Spin-Orbit Coupling With Quasidegenerate N-Electron Valence Perturbation Theory [77.34726150561087]
  We present the first implementation of spin-orbit coupling effects in SO-QDNEVPT2. The accuracy of these methods is tested for the group 14 and 16 hydrides, 3d and 4d transition metal ions, and two actinide dioxides.
  arXiv  Detail & Related papers  (2022-11-11T20:03:37Z)
• Spin Current Density Functional Theory of the Quantum Spin-Hall Phase [59.50307752165016]
  We apply the spin current density functional theory to the quantum spin-Hall phase. We show that the explicit account of spin currents in the electron-electron potential of the SCDFT is key to the appearance of a Dirac cone.
  arXiv  Detail & Related papers  (2022-08-29T20:46:26Z)
• Electron-Affinity Time-Dependent Density Functional Theory: Formalism and Applications to Core-Excited States [0.0]
  The particle-hole interaction problem is longstanding within time-dependent density functional theory. We derive a linear-response formalism that uses optimized orbitals of the n-1-electron system as reference. Our approach is an exact generalization of the static-exchange approximation and reduces errors in TDDFT XAS by orders of magnitude.
  arXiv  Detail & Related papers  (2022-05-17T23:05:15Z)
• Density Functional Theory Transformed into a One-electron Reduced Density Matrix Functional Theory for the Capture of Static Correlation [0.0]
  Density functional theory (DFT) fails to describe accurately the electronic structure of strongly correlated systems. We show that DFT can be transformed into a one-electron reduced-density-matrix (1-RDM) functional theory. Our approach yields substantial improvements over traditional DFT in the description of static correlation in chemical structures and processes.
  arXiv  Detail & Related papers  (2022-01-11T01:41:53Z)
• Quantum correlations, entanglement spectrum and coherence of two-particle reduced density matrix in the Extended Hubbard Model [62.997667081978825]
  We study the ground state properties of the one-dimensional extended Hubbard model at half-filling. In particular, in the superconducting region, we obtain that the entanglement spectrum signals a transition between a dominant singlet (SS) to triplet (TS) pairing ordering in the system.
  arXiv  Detail & Related papers  (2021-10-29T21:02:24Z)
• $\mathcal{P}$,$\mathcal{T}$-odd effects for RaOH molecule in the excited vibrational state [77.34726150561087]
  Triatomic molecule RaOH combines the advantages of laser-coolability and the spectrum with close opposite-parity doublets. We obtain the rovibrational wave functions of RaOH in the ground electronic state and excited vibrational state using the close-coupled equations derived from the adiabatic Hamiltonian.
  arXiv  Detail & Related papers  (2020-12-15T17:08:33Z)
• Excitation Energies from Thermally-Assisted-Occupation Density Functional Theory: Theory and Computational Implementation [0.0]
  We develop time-dependent (TD) TAO-DFT, which is a time-dependent, linear-response theory for excited states. TDTAO-DFT also yields zero singlet-triplet gap in the dissociation limit, for the ground singlet ($11Sigma_g+$) and the first triplet state ($13Sigma_u+$)
  arXiv  Detail & Related papers  (2020-07-15T10:12:59Z)

This list is automatically generated from the titles and abstracts of the papers in this site.

This site does not guarantee the quality of this site (including all information) and is not responsible for any consequences.