Related Experiment Video
Updated: Mar 29, 2026

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
A Multiconfigurational Perturbation Theory and Density Functional Theory Study on the Heterolytic Dissociation
Quan Manh Phung1, Steven Vancoillie1, Kristine Pierloot1
1Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001 Heverlee, Belgium.
Abstract:
The heterolytic dissociation enthalpy of a series of first-row metallocenes M(C5H5)2, M = V, Mn, Fe, and Ni, was studied by (restricted) multiconfigurational perturbation theory and density functional theory. The results were compared directly to the experimental values, taking into account all necessary contributions to the relative energy. Of the tested functionals, B3LYP performs best in reproducing the binding energy, while the PBE0 functional gives the best structures. High quality multiconfigurational perturbation calculations were also carried out, demonstrating the superior performance of a larger, restricted active space. The spin crossover behavior of manganocene is correctly predicted by multiconfigurational perturbation theory as opposed to the three functionals B3LYP, PBE0, and M06, which (severely) overstabilize the high-spin with respect to the low-spin state.
More Related Videos
16:11Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
10:52Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Related Concept Videos
Aromatic Hydrocarbon Cations: Structural Overview
Removing one hydrogen from the intervening CH2 group...
Cycloaddition Reactions: MO Requirements for Thermal Activation
Thermal and Photochemical Electrocyclic Reactions: Overview
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Complexation Equilibria: The Chelate Effect
Crystal Field Theory - Tetrahedral and Square Planar 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,...