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Crystal Field Theory - Octahedral Complexes

Crystal Field Theory - Octahedral Complexes

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...

Phase Transitions: Melting and Freezing

Phase Transitions: Melting and Freezing

Heating a crystalline solid increases the average energy of its atoms, molecules, or ions, and the solid gets hotter. At some point, the added energy becomes large enough to partially overcome the forces holding the molecules or ions of the solid in their fixed positions, and the solid begins the process of transitioning to the liquid state or melting. At this point, the temperature of the solid stops rising, despite the continual input of heat, and it remains constant until all of the solid is...

Colors and Magnetism

Colors and Magnetism

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 eye.

Crystal Field Theory - Tetrahedral and Square Planar Complexes

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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,...

Phase Transitions: Sublimation and Deposition

Phase Transitions: Sublimation and Deposition

Some solids can transition directly into the gaseous state, bypassing the liquid state, via a process known as sublimation. At room temperature and standard pressure, a piece of dry ice (solid CO2) sublimes, appearing to gradually disappear without ever forming any liquid. Snow and ice sublimate at temperatures below the melting point of water, a slow process that may be accelerated by winds and the reduced atmospheric pressures at high altitudes. When solid iodine is warmed, the solid sublimes...

Imperfections in Crystal Structure: Stoichiometric Point Defects

Imperfections in Crystal Structure: Stoichiometric Point Defects

Schottky defects arise when some lattice points in a crystal, such as those in NaCl, remain unoccupied, creating lattice vacancies without disturbing the overall electrical neutrality of the crystal. This defect is common in ionic crystals where the positive and negative ions are similar in size, as seen in sodium chloride and cesium chloride. The presence of Schottky defects enables the crystal to conduct electricity to a small extent through an ionic mechanism. Electric fields cause nearby...

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Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

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Photoinduced Structural Instability Toward the Superionic Phase Transition in Cu₂S.

Gaël Privault¹, Kaito En-Ya², Keito Sano³

¹Institute of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8573, Japan.

The Journal of Physical Chemistry Letters

|June 26, 2026

Summary

This summary is machine-generated.

Photoexcitation rapidly destabilizes copper ordering in copper(I) sulfide (Cu2S), initiating its transition to a superionic phase. This ultrafast process, observed via time-resolved electron diffraction, reveals key dynamics in superionic materials.

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Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

Published on: June 7, 2018

Area of Science:

Materials Science
Solid-State Physics
Photochemistry

Background:

Copper(I) sulfide (Cu2S) exhibits a semiconductor-to-superionic phase transition.
This transition involves the destabilization of the ordered copper (Cu) sublattice.
Understanding the dynamics of this transition is crucial for developing advanced materials.

Purpose of the Study:

To investigate the structural dynamics of photoexcited Cu2S.
To elucidate the ultrafast microscopic pathway toward the superionic phase.
To provide insights into photoinduced structural dynamics in superionic materials.

Main Methods:

Time-resolved electron diffraction (picoseconds to milliseconds).
Fluence-dependent measurements to identify thresholds.
Density functional theory (DFT) calculations.

Main Results:

Rapid suppression (80%-90%) of semiconducting phase superlattice reflections within ~10 ps.
Prompt destabilization of Cu ordering observed.
Slower lattice expansion (~100 ps) and lattice strain (~0.7%) detected.
Fluence threshold identified for sublattice destabilization.
DFT calculations confirm photoexcitation populates antibonding states, weakening Cu-S bonds.

Conclusions:

Photoexcitation promptly destabilizes the ordered Cu sublattice in Cu2S.
Ultrafast microscopic pathway toward the superionic phase is revealed.
Findings offer insights into photoinduced structural dynamics in superionic materials.