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The Energies of Atomic Orbitals03:21

The Energies of Atomic Orbitals

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In an atom, the negatively charged electrons are attracted to the positively charged nucleus. In a multielectron atom, electron-electron repulsions are also observed. The attractive and repulsive forces are dependent on the distance between the particles, as well as the sign and magnitude of the charges on the individual particles. When the charges on the particles are opposite, they attract each other. If both particles have the same charge, they repel each other.
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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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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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The Quantum-Mechanical Model of an Atom02:45

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Shortly after de Broglie published his ideas that the electron in a hydrogen atom could be better thought of as being a circular standing wave instead of a particle moving in quantized circular orbits, Erwin Schrödinger extended de Broglie’s work by deriving what is now known as the Schrödinger equation. When Schrödinger applied his equation to hydrogen-like atoms, he was able to reproduce Bohr’s expression for the energy and, thus, the Rydberg formula governing hydrogen spectra.
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IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration01:16

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A covalently bonded heteronuclear diatomic molecule can be modeled as two vibrating masses connected by a spring. The vibrational frequency of the bond can be expressed using an equation derived from Hooke's law, which describes how the force applied to stretch or compress a spring is proportional to the displacement of the spring. In this case, the atoms behave like masses, and the bond acts like a spring.
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Free Energy Changes for Nonstandard States03:25

Free Energy Changes for Nonstandard States

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The free energy change for a process taking place with reactants and products present under nonstandard conditions (pressures other than 1 bar; concentrations other than 1 M) is related to the standard free energy change according to this equation:
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Related Experiment Video

Updated: Nov 10, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

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Short-range DFT energy correction to multiconfigurational wave functions for open-shell systems.

José Aarón Rodríguez-Jiménez1, Abel Carreras1, David Casanova1

  • 1Donostia International Physics Center (DIPC), 20080 Donostia, Euskadi, Spain.

The Journal of Chemical Physics
|April 3, 2021
PubMed
Summary
This summary is machine-generated.

This study reveals limitations of wave function theory combined with density functional theory (WFT-DFT) for open-shell systems. Incorporating spin polarization effects significantly improves the description of these challenging electronic structures.

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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
  • Quantum chemistry
  • Electronic structure theory

Background:

  • Combining multiconfigurational wave functions and density functional theory (DFT) aims to leverage the strengths of both approaches.
  • Wave Function Theory (WFT) combined with DFT (WFT-srDFT) often uses range separation, with DFT handling short-range interactions and WFT handling long-range ones.

Purpose of the Study:

  • To uncover the limitations of WFT-srDFT in characterizing open-shell systems.
  • To introduce and test strategies for accounting for spin polarization in WFT-srDFT.

Main Methods:

  • Investigated the impact of spin polarization on short-range DFT exchange energy.
  • Developed methods using spin-polarized electron density and short-range exact exchange.
  • Tested approaches on H2 dissociation, triplet atom/diradical energy gaps, and Ga2 low-lying states.

Main Results:

  • Spin polarization significantly affects short-range DFT exchange energy, crucial for open-shell systems.
  • The proposed spin-polarized WFT-srDFT methods improve the description of open-shell systems.
  • Combining short-range DFT correlation with full-range WFT shows promise for open-shell molecules.

Conclusions:

  • WFT-srDFT methods require explicit treatment of spin polarization for accurate open-shell system characterization.
  • The developed spin-polarized approaches enhance the performance of WFT and WFT-srDFT.
  • Short-range DFT correlation with full-range WFT offers a promising avenue for studying open-shell molecules.