Ligand field stabilization energies, is it correct to say

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Discussion Overview

The discussion revolves around ligand field stabilization energies in transition metal complexes, particularly focusing on low-spin d5 and d6 metals. Participants explore the relationship between ligand field stabilization, electron affinity, and pairing energy, considering various factors that influence these energies.

Discussion Character

  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant proposes a formula for the energy of low-spin d5 and d6 metals, suggesting that the energy needed to add an electron can be expressed as ΔE = 0.4Δ + K.
  • Another participant argues that the energy to add an extra electron (electron affinity) is influenced more by factors other than ligand field stabilization, highlighting the role of intraatomic electron repulsion.
  • A subsequent post questions whether the increased intraatomic repulsion is related to pairing energy, indicating that pairing energy contributes but may be a small factor.
  • Further elaboration includes a suggestion to consider a Born cycle to analyze the energy changes involved in complex formation and electron addition, emphasizing that ligand field stabilization is only one aspect of the overall energy considerations.

Areas of Agreement / Disagreement

Participants express differing views on the significance of ligand field stabilization in determining electron affinity, with no consensus reached on the primary factors influencing these energies.

Contextual Notes

Participants note that the discussion lacks specificity regarding the concrete situations being analyzed, such as the coordination of the complex and the exact nature of the electron addition process.

Chemist20
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the following?:

low-spin d5 metal. Energy = -2Δ -4K (where K is exchange energy. i,e. minimization of energy due to parallel spins)

low-spin d6 metal. Energy = -1.6Δ -3K

Therefore: energy needed to add an electron = ΔE= 0.4Δ + K

Is that correct?

maybe I should be talking about Spin Pairing Energy (P) ...

HEEEEEEEEEEEEEEEEEEEEEEEEEEEELP!:cry:
 
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The energy to add an extra electron (i.e. electron affinity) depends much more on other factors than ligand field stabilization. This should already be clear from the fact that electron affinity is not zero for atoms in the gas phase where there is no ligand field stabilization.
It mainly depends on the increased intraatomic repulsion of the electrons.
 
DrDu said:
The energy to add an extra electron (i.e. electron affinity) depends much more on other factors than ligand field stabilization. This should already be clear from the fact that electron affinity is not zero for atoms in the gas phase where there is no ligand field stabilization.
It mainly depends on the increased intraatomic repulsion of the electrons.

that would be the pairing energy right?
 
Chemist20 said:
that would be the pairing energy right?

The pairing energy would also contribute, but this contribution would be rather small.
Your question is not very specific. What is the concrete situation you have in mind? It would also be helpful to specify the coordination of the complex ...

I would consider some Born cycle, i.e. desolvation of the complex ion, decomplexation of the ion with charge i+1, electron affinity of the ion, formation of the complex with charge i, solvation of the complex. Similar cycle for the ion or atom delivering the electron.
The ligand field statilization only contribute to the second and before last step.
The ligand field stabilization is only a relative stabilization of some set of d orbitals relative to others. Even in a complex where there is no ligand field effect, like going from s^0 to s^1, the energy of complex formation is generally non-zero, e.g. due to the increasing (or decreasing) electrostatic attraction between the central atom and the ligands.
 

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