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Crystal Field Theory - Octahedral Complexes02:58

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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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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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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

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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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Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
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Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
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Related Experiment Video

Updated: Jan 12, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F&#8722;
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Excited State Assignment and State-Resolved Photoelectron Circular Dichroism in Chalcogen-Substituted Fenchones.

Sudheendran Vasudevan1, Steffen M Giesen2, Simon T Ranecky1

  • 1Institut für Physik and CINSaT, Universität Kassel, Heinrich-Plett-Str. 40, 34132, Kassel, Germany.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
|November 3, 2025
PubMed
Summary
This summary is machine-generated.

Chirality in fenchone derivatives is revealed using advanced spectroscopy. Increasing atomic number of chalcogens causes red shifts, impacting molecular chirality measurements.

Keywords:
chiralitycircular dichroismfemtochemistrylight‐matter interactionsphotoelectron spectroscopy

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Area of Science:

  • Physical Chemistry
  • Spectroscopy
  • Quantum Chemistry

Background:

  • Fenchone, thiofenchone, and selenofenchone are sulfur and selenium analogs of camphor.
  • Understanding their electronic excited states is crucial for molecular chirality studies.

Purpose of the Study:

  • To characterize and assign the excited electronic states of fenchone, thiofenchone, and selenofenchone.
  • To investigate the influence of chalcogen substitution on electronic properties.
  • To utilize spectroscopic insights for state-resolved circular dichroism measurements.

Main Methods:

  • Gas-phase spectroscopic techniques.
  • Ab initio quantum chemical calculations.
  • Femtosecond laser pulse multiphoton photoelectron circular dichroism.

Main Results:

  • Observed bathochromic (red) shifts with increasing chalcogen atomic number for Rydberg and valence-excited states.
  • Ionization energies also exhibit shifts correlated with chalcogen identity.
  • Multiphoton photoelectron circular dichroism proves sensitive to molecular chirality in all studied compounds.

Conclusions:

  • New spectroscopic data for thiofenchone and selenofenchone are presented.
  • Electronic state characterization provides a basis for understanding chirality.
  • Potential for future coherent control experiments in visible and near-UV regions.