Related Experiment Video
Updated: Jul 19, 2026
06:53
Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach
Heather J Kulik1, Matteo Cococcioni, Damian A Scherlis
1Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Physical Review Letters
|October 10, 2006
Summary
Density-functional theory often fails for transition metals. A Hubbard U correction method improves accuracy for energetics and reaction barriers in transition metal chemistry.
Area of Science:
- Inorganic chemistry
- Computational chemistry
- Quantum chemistry
Background:
- Transition-metal centers are crucial active sites in numerous biological and inorganic reactions.
- Standard density-functional theory (DFT) methods, particularly generalized-gradient approximations (GGAs), often exhibit limitations in accurately describing transition-metal systems.
- These limitations include inaccuracies in energetics, multiplet structures, reaction barriers, and active site geometries.
Purpose of the Study:
- To introduce and validate an alternative computational approach for transition-metal systems.
- To address the shortcomings of conventional DFT methods in describing the electronic and reactive properties of transition metals.
Main Methods:
- The study proposes an approach derived from the Hubbard U correction, a method typically used in solid-state physics.
- A novel self-consistent procedure, based on a linear-response approach, is employed to determine the Hubbard U values.
- The method's efficacy is tested against established correlated-electron quantum chemistry calculations.
Main Results:
- The Hubbard U correction approach demonstrates excellent agreement with high-level correlated-electron quantum chemistry calculations.
- Accurate predictions were achieved for various test cases, including the ground states of Fe2 and Fe2-.
- The method successfully modeled the addition-elimination of molecular hydrogen on FeO+.
Conclusions:
- The Hubbard U correction, determined via a linear-response self-consistent procedure, offers a significant improvement over standard GGAs for transition-metal chemistry.
- This approach provides a more reliable and accurate computational tool for studying the energetics, electronic structure, and reactivity of transition-metal active sites.
- The validated method holds promise for advancing research in catalysis, bioinorganic chemistry, and materials science involving transition metals.
More Related Videos
Related Concept Videos
02:58Crystal Field Theory - Octahedral Complexes
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
02:42Valence Bond Theory
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
02:45Valence Bond Theory
Overview of Valence Bond Theory
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
02:46Electron Configurations
Electron configurations and orbital diagrams can be determined by applying the Aufbau principle (each added electron occupies the subshell of lowest energy available), Pauli exclusion principle (no two electrons can have the same set of four quantum numbers), and Hund’s rule of maximum multiplicity (whenever possible, electrons retain unpaired spins in degenerate orbitals).
The relative energies of the subshells determine the order in which atomic orbitals are filled (1s, 2s, 2p, 3s, 3p, 4s,...
The relative energies of the subshells determine the order in which atomic orbitals are filled (1s, 2s, 2p, 3s, 3p, 4s,...
02:58Properties of Transition Metals
Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.