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X-ray Crystallography02:18

X-ray Crystallography

24.1K
The size of the unit cell and the arrangement of atoms in a crystal may be determined from measurements of the diffraction of X-rays by the crystal, termed X-ray crystallography.
Diffraction
Diffraction is the change in the direction of travel experienced by an electromagnetic wave when it encounters a physical barrier whose dimensions are comparable to those of the wavelength of the light. X-rays are electromagnetic radiation with wavelengths about as long as the distance between neighboring...
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Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

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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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Atomic Spectroscopy: Absorption, Emission, and Fluorescence01:23

Atomic Spectroscopy: Absorption, Emission, and Fluorescence

1.2K
Atomic spectroscopy is a vital tool in elemental analysis, both qualitatively and quantitatively. It can be broadly divided into optical spectroscopy, mass spectroscopy, and X-ray spectroscopy methods. The optical spectroscopic methods are atomic absorption spectroscopy (AAS), atomic emission spectroscopy (AES), and atomic fluorescence spectroscopy (AFS). The first step in all three methods is atomization, where the solid, liquid, or solution-phase samples are converted into gas-phase atoms and...
1.2K
Atomic Nuclei: Types of Nuclear Relaxation01:28

Atomic Nuclei: Types of Nuclear Relaxation

365
Nuclear relaxation restores the equilibrium population imbalance and can occur via spin–lattice or spin–spin mechanisms, which are first-order exponential decay processes.
In spin–lattice or longitudinal relaxation, the excited spins exchange energy with the surrounding lattice as they return to the lower energy level. Among several mechanisms that contribute to spin–lattice relaxation, magnetic dipolar interactions are significant. Here, the excited nucleus transfers...
365
¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

1.1K
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...
1.1K
X-ray Diffraction of Biological Samples01:10

X-ray Diffraction of Biological Samples

3.9K
X-ray diffraction or XRD is an analytical tool that utilizes X-rays to study ordered structures such as crystalline organic and inorganic samples, polycrystalline materials, proteins, carbohydrates, and drugs.
According to Bragg's law, when X-rays strike the sample positioned on a stage, the rays are  scattered by the electron clouds around the sample atoms. The  X-ray diffraction or scattering is caused by constructive interference of the X-ray waves that reflect off the internal...
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Related Experiment Video

Updated: Aug 27, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

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Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory for Accurate X-ray Absorption Spectroscopy.

Woojin Park1, Marc Alías-Rodríguez2, Daeheum Cho1

  • 1Department of Chemistry, Kyungpook National University, Daegu 41566, South Korea.

Journal of Chemical Theory and Computation
|September 27, 2022
PubMed
Summary
This summary is machine-generated.

Mixed-reference spin-flip (MRSF)-time-dependent density functional theory (TDDFT) accurately predicts core-hole particle (CHP) orbital relaxation in core electron spectra. This method offers high precision for K-edge excitation energies, outperforming relativistic effects.

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Area of Science:

  • Quantum Chemistry
  • Computational Spectroscopy
  • Theoretical Chemistry

Background:

  • Core electron spectra are crucial for understanding molecular electronic structure.
  • Accurately modeling core-hole particle (CHP) orbital relaxation is computationally challenging.
  • Relativistic effects also influence core electron spectra, particularly for heavier elements.

Purpose of the Study:

  • To demonstrate the efficacy of mixed-reference spin-flip (MRSF)-time-dependent density functional theory (TDDFT) for calculating core electron spectra.
  • To investigate the contribution of CHP orbital relaxation and scalar relativistic effects on K-edge excitation energies.
  • To validate the MRSF-TDDFT protocol for both ground and excited electronic states.

Main Methods:

  • Application of the ΔCHP-MRSF(R) protocol within TDDFT.
  • Inclusion of scalar relativistic effects for K-edge excitation energies.
  • Utilizing a double hole-particle relaxation for core-to-valence excitations.

Main Results:

  • The ΔCHP-MRSF(R) method achieved high accuracy for K-edge excitation energies (RMSE ~0.5 eV).
  • CHP orbital relaxation was found to be significantly stronger (2-4 times) than relativistic effects.
  • Precise spectral assignments were made for O, N, and C K-edges in thymine, including excited states.

Conclusions:

  • MRSF-TDDFT provides a highly accurate and practical protocol for core electron spectra.
  • The method successfully models both ground and excited electronic states.
  • This approach enables detailed analysis of spectral features with atom and orbital specificity.