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Related Concept Videos

Atomic Orbitals02:44

Atomic Orbitals

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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Hybridization of Atomic Orbitals II

sp3d and sp3d 2 Hybridization
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Spin–Spin Coupling Constant: Overview

In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must have a...
Hybridization of Atomic Orbitals I03:24

Hybridization of Atomic Orbitals I

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...
Valence Bond Theory and Hybridized Orbitals02:38

Valence Bond Theory and Hybridized Orbitals

According to valence bond theory, a covalent bond results when: (1) an orbital on one atom overlaps an orbital on a second atom, and (2) the single electrons in each orbital combine to form an electron pair. The strength of a covalent bond depends on the extent of overlap of the orbitals involved. Maximum overlap is possible when the orbitals overlap on a direct line between the two nuclei.
A σ bond (single bond in a Lewis structure) is a covalent bond in which the electron density is...
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...

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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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Spin-state-corrected Gaussian-type orbital basis sets.

Marcel Swart1, Mireia Güell, Josep M Luis

  • 1Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Spain.

The Journal of Physical Chemistry. A
|June 18, 2010
PubMed
Summary
This summary is machine-generated.

Modified small Gaussian-type orbital (GTO) basis sets improve spin-state energy predictions for transition-metal complexes. These corrected basis sets (s6-31G, s6-31G*) accurately predict spin ground states, unlike original or modified sets.

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Materials Science

Background:

  • Basis sets significantly impact computed spin-state splittings in quantum chemical calculations.
  • Small Gaussian-type orbital (GTO) basis sets have demonstrated unreliability for predicting these spin-state properties.
  • Accurate prediction of spin states is crucial for understanding and designing transition-metal complexes.

Purpose of the Study:

  • To develop simple modifications for small Pople-type GTO basis sets (3-21G, 3-21G*, 6-31G, 6-31G*) to correct their inaccuracies in spin-state energy calculations.
  • To evaluate the performance of these modified basis sets against reliable reference data for first-row transition-metal complexes.
  • To assess the impact of the modifications on geometry optimization and vibrational frequency calculations.

Main Methods:

  • Investigated 13 first-row transition-metal complexes using modified Pople-type GTO basis sets (s6-31G, s6-31G*).
  • Utilized spin-contamination corrections (single and double) to ensure calculations were performed for pure spin states.
  • Compared results with high-level reference data obtained at the OPBE/TZ2P(STO) level.

Main Results:

  • The spin-state-corrected GTO basis sets (s6-31G, s6-31G*) achieved complete agreement with Slater-type orbital (STO) reference data for spin ground states.
  • Original Pople-type basis sets and a modified version (m6-31G*) failed to consistently predict the correct spin ground states.
  • The corrected basis sets also enhanced the accuracy of geometry optimizations and maintained or improved vibrational frequency calculations.

Conclusions:

  • Simple modifications to small GTO basis sets can effectively correct their deficiencies in calculating spin-state energies for transition-metal complexes.
  • The s6-31G and s6-31G* basis sets offer a reliable and cost-effective alternative for accurate spin-state energy predictions.
  • These improved basis sets provide more accurate geometries and vibrational frequencies with minimal additional computational cost.