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Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

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

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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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,...
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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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...
20.6K
Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
468
Valence Bond Theory02:42

Valence Bond Theory

8.5K
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...
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Bonding in Metals02:32

Bonding in Metals

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Metallic bonds are formed between two metal atoms. A simplified model to describe metallic bonding has been developed by Paul Drüde called the “Electron Sea Model”. 
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Updated: Jun 10, 2025

Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
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Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides

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A Constrained CASSCF(2,2) Approach to Study Electron Transfer between a Molecule and Metal Cluster.

Xinchun Wu1,2, Junhan Chen1,2, Joseph Subotnik1,2

  • 1Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.

The Journal of Physical Chemistry. A
|October 21, 2024
PubMed
Summary

We studied thermal electron transfer between chlorine ions and lithium clusters. Cluster size and ion positioning significantly impact electron transfer, paving the way for modeling complex electrochemical systems.

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

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Area of Science:

  • Computational chemistry
  • Physical chemistry
  • Quantum chemistry

Background:

  • Electron transfer is fundamental to chemical reactions.
  • Understanding homogeneous vs. heterogeneous electron transfer is crucial.
  • Computational modeling aids in studying complex chemical systems.

Purpose of the Study:

  • To investigate thermal electron transfer between a chlorine ion and lithium clusters.
  • To analyze the influence of cluster size and geometry on electron transfer dynamics.
  • To establish a computational foundation for studying heterogeneous electron transfer.

Main Methods:

  • Constrained Configuration Interaction Self-Consistent Field (CASSCF) calculations.
  • Utilized a CASSCF(2,2) level of theory.
  • Varied lithium cluster size from 1 to 17 atoms.

Main Results:

  • Demonstrated sensitive dependence of the ground state-charge transfer crossing point geometry on cluster size.
  • Showcased how diabatic coupling strength is affected by the number of lithium ions.
  • Highlighted the role of donor-acceptor relative positioning in electron transfer.
  • Identified key factors influencing the transition from homogeneous to heterogeneous electron transfer.

Conclusions:

  • The size and geometry of lithium clusters critically influence electron transfer with chlorine ions.
  • Constrained CASSCF calculations provide a scalable method for studying larger systems.
  • This research serves as a stepping stone towards modeling electrochemical phenomena computationally.