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Atomic Orbitals02:44

Atomic Orbitals

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An atomic orbital represents the three-dimensional regions in an atom where an electron has the highest probability to reside. The radial distribution function indicates the total probability of finding an electron within the thin shell at a distance r from the nucleus. The atomic orbitals have distinct shapes which are determined by l, the angular momentum quantum number. The orbitals are often drawn with a boundary surface, enclosing densest regions of the cloud.
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Electron Configuration of Multielectron Atoms03:26

Electron Configuration of Multielectron Atoms

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The alkali metal sodium (atomic number 11) has one more electron than the neon atom. This electron must go into the lowest-energy subshell available, the 3s orbital, giving a 1s22s22p63s1 configuration. The electrons occupying the outermost shell orbital(s) (highest value of n) are called valence electrons, and those occupying the inner shell orbitals are called core electrons. Since the core electron shells correspond to noble gas electron configurations, we can abbreviate electron...
60.7K
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.
27.3K
Trends in Lattice Energy: Ion Size and Charge02:54

Trends in Lattice Energy: Ion Size and Charge

25.1K
An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid sodium chloride, the lattice energy is the enthalpy change of the process:
25.1K
Electronic Structure of Atoms02:28

Electronic Structure of Atoms

25.5K

An atom comprises protons and neutrons, which are contained inside the dense, central core called the nucleus, with electrons present around the nucleus. Taking into account the wave–particle duality of electrons and the uncertainty in position around the nucleus, quantum mechanics provides a more accurate model for the atomic structure. It describes atomic orbitals as the regions around the nucleus where electrons of discrete energy exist, characterized by four quantum...
25.5K
Hybridization of Atomic Orbitals I03:24

Hybridization of Atomic Orbitals I

52.6K
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
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Updated: Oct 18, 2025

Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals
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Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals

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Property-optimized Gaussian basis sets for lanthanides.

Dmitrij Rappoport1

  • 1Department of Chemistry, University of California, Irvine, California 92697, USA.

The Journal of Chemical Physics
|October 2, 2021
PubMed
Summary
This summary is machine-generated.

New Gaussian basis sets for lanthanides (Ce-Lu) improve atomic and molecular property calculations. These property-optimized sets, including split-valence, triple-zeta, and quadruple-zeta qualities, enhance accuracy in electronic absorption spectra predictions.

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Preparation, Purification, and Characterization of Lanthanide Complexes for Use as Contrast Agents for Magnetic Resonance Imaging
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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Atomic and Molecular Physics

Background:

  • Accurate computational modeling of lanthanide elements is crucial for understanding their chemical properties.
  • Existing Gaussian basis sets often require optimization for specific properties like polarizability.
  • Relativistic effects and f-electron behavior in lanthanides present unique computational challenges.

Purpose of the Study:

  • To develop property-optimized Gaussian basis sets for lanthanides (Ce-Lu).
  • To improve the accuracy of calculations involving lanthanide atoms and molecules.
  • To provide reliable basis sets for predicting electronic absorption spectra.

Main Methods:

  • Systematic augmentation of existing def2 basis sets with diffuse functions.
  • Minimization of negative static isotropic polarizabilities using the unrestricted Hartree-Fock method.
  • Assessment using a test set of 70 lanthanide-containing molecules and electronic absorption spectra calculations.

Main Results:

  • Developed split-valence, triple-zeta, and quadruple-zeta quality basis sets (def2-SVPD, def2-TZVPPD, def2-QZVPPD).
  • Achieved relative errors in polarizability calculations of ≤8% (SVPD), ≤2.5% (TZVPPD), and ≤1% (QZVPPD).
  • Demonstrated accurate reproduction of electronic absorption spectra for LnCp'3 complexes.

Conclusions:

  • The new property-optimized basis sets offer significant improvements in accuracy for lanthanide calculations.
  • 5d orbital occupation is identified as a key factor for basis set convergence in polarizability.
  • These basis sets are valuable tools for theoretical studies of lanthanide chemistry and spectroscopy.