Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Concept Videos

Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

28.4K
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...
28.4K
Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

45.4K
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,...
45.4K
Valence Bond Theory02:42

Valence Bond Theory

9.8K
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...
9.8K
Properties of Transition Metals02:58

Properties of Transition Metals

27.8K
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.
27.8K
Ladder Diagrams: Complexation Equilibria01:07

Ladder Diagrams: Complexation Equilibria

451
Ladder diagrams are useful for evaluating equilibria involving metal-ligand complexes. The vertical scale of the ladder diagram represents the concentration of unreacted or free ligand, pL. The horizontal lines on the scale depict the log of stepwise formation constants for metal-ligand complexes and indicate the dominant species in all the regions.
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...
451
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

22.3K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
22.3K

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

From Sequential Molecular Adsorption on Atomically Precise Ag<sub>29</sub> Nanoclusters to Aggregates of Soot-Like Particles.

ACS nano·2026
Same author

Steric Mapping, Ligand Dynamics, and Cycloisomerization Catalysis with Redox Robust Mn<sup>I/0/‑I</sup> Dicarbenes.

Organometallics·2026
Same author

A Molecular "Thermometer" for Measuring Effective Non-Local Exchange.

Journal of computational chemistry·2026
Same author

Structural Localization of Mass-Degenerate Intact tRNA<sup>PHE</sup> Species by Ion-Pair UHPLC-HRMS and CID-MS<sup>3</sup>.

Analytical chemistry·2026
Same author

A Ruthenium-(Ph-BPE) Catalyst for Asymmetric Alkynylation of Fluoral: Enantioselection From 1 of 12 Fluxional Stereogenic-at-Ruthenium Complexes.

Angewandte Chemie (International ed. in English)·2026
Same author

How Spin Conductive are Oligo(p-phenylenes) in Trityl-Based Biradicals.

Journal of the American Chemical Society·2026

Related Experiment Video

Updated: Oct 19, 2025

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics
10:52

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

Published on: April 12, 2019

13.0K

Assessing Density Functional Theory for Chemically Relevant Open-Shell Transition Metal Reactions.

Leonard R Maurer1, Markus Bursch1, Stefan Grimme1

  • 1Mulliken Center for Theoretical Chemistry, Institute for Physical and Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115 Bonn, Germany.

Journal of Chemical Theory and Computation
|September 21, 2021
PubMed
Summary

A new benchmark set, ROST61, evaluates density functional approximations (DFAs) for open-shell transition metal chemistry. London dispersion corrections significantly improve DFA performance, with double-hybrid DFAs showing the highest accuracy for reaction energies.

More Related Videos

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
16:11

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry

Published on: June 8, 2022

2.4K
Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
12:11

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

8.4K

Related Experiment Videos

Last Updated: Oct 19, 2025

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics
10:52

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

Published on: April 12, 2019

13.0K
Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
16:11

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry

Published on: June 8, 2022

2.4K
Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
12:11

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

8.4K

Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Materials Science

Background:

  • Density functional theory (DFT) requires systematic assessment for reliable chemical predictions.
  • Existing benchmark sets primarily cover main-group chemistry, leaving transition metal chemistry underrepresented.
  • Accurate data for larger, chemically relevant open-shell transition metal complexes is particularly scarce.

Purpose of the Study:

  • To introduce the ROST61 benchmark set for evaluating density functional approximations (DFAs) on open-shell transition metal complexes.
  • To extend benchmark data beyond closed-shell systems and main-group elements.
  • To assess the performance of various DFAs, composite methods, and dispersion corrections for reaction energies.

Main Methods:

  • Development of the ROST61 benchmark set comprising 61 reaction energies for open-shell transition metal complexes.
  • Calculation of accurate coupled-cluster reference values for the benchmark set.
  • Evaluation of 31 DFAs with three London dispersion (LD) correction schemes, DFT-based composite methods, MP2, and semiempirical methods.

Main Results:

  • The ROST61 set includes complexes with 13-93 atoms across 20 d-block elements.
  • London dispersion corrections were found to be crucial, improving the performance of most tested methods.
  • The r2SCAN-3c composite method achieved a mean absolute deviation (MAD) of 2.9 kcal mol-1, while double-hybrid DFAs like PWPB95-D4 reached 1.6 kcal mol-1.

Conclusions:

  • The ROST61 benchmark set provides essential reference data for the under-sampled area of open-shell transition metal chemistry.
  • The study confirms the preservation of DFA performance ordering based on Jacob's ladder.
  • The findings offer valuable guidance for the application and development of DFAs and electronic structure methods for transition metal systems.