It is often stated that the exact Kohn-Sham HOMO-LUMO gap underestimates the fundamental gap. Here, using the Hubbard dimer as a model Hamiltonian, we show numerically that the exact Kohn-Sham gap can be larger than the fundamental gap.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/d4cp02688h | DOI Listing |
J Chem Theory Comput
October 2024
School of Physics, Beihang University, Beijing 100191, China.
We present the implementation of the Hubbard () and Hund () corrected Density Functional Theory (DFT + + ) functionality in the Quickstep program, which is part of the CP2K suite. The tensorial and Löwdin subspace representations are implemented and compared. Full analytical DFT + + forces are implemented and benchmarked for the tensorial and Löwdin representations.
View Article and Find Full Text PDFPhys Chem Chem Phys
September 2024
School of Physics, University of the Witwatersrand, P.O. Wits, Johannesburg 2050, South Africa.
It is often stated that the exact Kohn-Sham HOMO-LUMO gap underestimates the fundamental gap. Here, using the Hubbard dimer as a model Hamiltonian, we show numerically that the exact Kohn-Sham gap can be larger than the fundamental gap.
View Article and Find Full Text PDFJ Chem Theory Comput
September 2024
Department of Chemistry, McGill University, 801 Sherbrooke St West, Montreal, QC H3A 0B8, Canada.
One-electron orbitals in Kohn-Sham density functional theory (DFT) are typically constrained to be orthogonal during their variational optimization, leading to elaborate parameterization of the orbitals and complicated optimization algorithms. This work shows that orbital optimization can be performed with nonorthogonal orbitals if the DFT energy functional is augmented with a term that penalizes linearly dependent states. This approach, called variable-metric self-consistent field (VM SCF) optimization, allows us to use molecular orbital coefficients, natural descriptors of one-electron orbitals, as independent variables in a direct, unconstrained minimization, leading to very simple closed-form expressions for the electronic gradient and Hessian.
View Article and Find Full Text PDFFaraday Discuss
November 2024
Laboratoire de Chimie Théorique, Sorbonne Université, CNRS, 4 Pl. Jussieu, 75005, Paris, France.
Analyzing the electronic localization of superconductors has been recently shown to be relevant for understanding their critical temperature [, , 5381, (2021)]. However, these relationships have only been shown at the Kohn-Sham density functional theory (DFT) level, where the onset of strong correlation linked to the superconducting state is missing. In this contribution, we approximate the superconducting gap in order to reconstruct the superconducting the one-reduced density matrix (1RDM) from a DFT calculation.
View Article and Find Full Text PDFJ Phys Chem Lett
August 2024
Mulliken Center for Theoretical Chemistry, Clausius Institute for Physical and Theoretical Chemistry, Rheinische Friedrich-Wilhelms Universität Bonn, Beringstraße 4, 53115 Bonn, Germany.
Efficient OLEDs need to quickly convert singlet and triplet excitons into photons. Molecules with an inverted singlet-triplet energy gap (INVEST) are promising candidates for this task. However, typical INVEST molecules have drawbacks like too low oscillator strengths and excitation energies.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!