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Related Concept Videos

Valence Bond Theory02:42

Valence Bond Theory

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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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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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Colors and Magnetism03:02

Colors and Magnetism

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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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Spin–Spin Coupling Constant: Overview01:08

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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.
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¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

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Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...
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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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Correcting Systematic Errors in DFT Spin-Splitting Energetics for Transition Metal Complexes.

Thomas F Hughes1, Richard A Friesner1

  • 1Columbia University, Department of Chemistry, New York, New York 10027, United States.

Journal of Chemical Theory and Computation
|November 26, 2015
PubMed
Summary
This summary is machine-generated.

Density functional theory (DFT) calculations for transition metal complexes are improved using a localized orbital correction (LOC) model. This DBLOC-DFT approach significantly reduces errors in predicting spin-splittings compared to experimental data.

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Spectroscopy

Background:

  • Accurate prediction of spin-splittings in transition metal complexes is crucial for understanding their electronic structure and properties.
  • Conventional density functional theory (DFT) methods, like B3LYP, often exhibit significant errors when compared to experimental spectra.
  • Ligand field theory provides a framework for initial state assignments but requires refinement for quantitative accuracy.

Purpose of the Study:

  • To develop and validate a novel computational model for improving the accuracy of spin-splitting calculations in first-row transition metal complexes.
  • To systematically correct B3LYP DFT calculations using a localized orbital correction (LOC) model, termed DBLOC-DFT.
  • To assess the performance of the DBLOC-DFT model against a comprehensive database of experimental electronic spectra.

Main Methods:

  • Calculations were performed on 57 octahedral first-row transition metal complexes using the B3LYP functional.
  • A localized orbital correction (LOC) model, DBLOC-DFT, was developed, incorporating five empirical parameters.
  • Environmental effects were included, and initial state guesses were derived from ligand field theory.
  • The corrected calculations were compared to experimental spin-splitting data from the literature.

Main Results:

  • The DBLOC-DFT model significantly reduced the mean unsigned error (MUE) in spin-splitting predictions from 10.14 kcal/mol to 1.98 kcal/mol.
  • The standard deviation of the error decreased from 4.56 to 1.62 kcal/mol, indicating improved quantitative agreement.
  • B3LYP with 15% exact exchange (B3LYP*) sometimes yielded larger errors than standard B3LYP, depending on state multiplicities.
  • The DBLOC model demonstrated good agreement with experimental data for spin-crossover complexes and other transition metal systems.

Conclusions:

  • The DBLOC-DFT approach offers a substantial improvement over conventional DFT methods for calculating spin-splittings in transition metal complexes.
  • This corrected DFT method provides reliable quantitative predictions, facilitating the interpretation of experimental spectra and the design of new materials.
  • The study highlights the importance of localized orbital corrections for achieving high accuracy in computational spectroscopy of d-block elements.