Related Experiment Video

Updated: Jun 29, 2025

Molecular Beam Mass Spectrometry With Tunable Vacuum Ultraviolet VUV Synchrotron Radiation

Molecular Beam Mass Spectrometry With Tunable Vacuum Ultraviolet VUV Synchrotron Radiation

Published on: October 30, 2012

Unveiling Hidden Shake-Up Features in the Uranyl M₄-Edge Spectrum

Jordan N Ehrman¹, Kirill Shumilov¹, Andrew J Jenkins¹

¹Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.

|April 1, 2024

Summary

High-resolution X-ray absorption spectroscopy of actinyls reveals electronic structure. Advanced computational methods accurately predict uranyl M4-edge spectra, including key shake-up features.

Area of Science:

Atomic and Molecular Physics
Computational Chemistry
Solid State Physics

Background:

Actinyls are heavy-element complexes with unique electronic structures.
Understanding their bonding and reactivity is crucial for various applications.
X-ray absorption near-edge structure (XANES) spectroscopy provides insights into electronic configurations.

Purpose of the Study:

To computationally investigate the M4,5-edge high energy resolution X-ray absorption near-edge structure (HR-XANES) spectra of actinyls.
To accurately model the electronic structure and bonding properties of heavy-element complexes.
To establish M4,5-edge spectroscopy as a tool for studying chemical activities of actinyls.

Main Methods:

Utilized variational relativistic multireference configurational interaction methods.
Computed and analyzed the X-ray M4-edge absorption spectrum of uranyl.
Employed advanced computational techniques accounting for relativistic effects and electron correlation.

Main Results:

Achieved excellent agreement between calculated spectral features and experimental observations for uranyl.
Unveiled significant shake-up features in the M4-edge absorption spectrum.
Demonstrated the interplay between core-electron and ligand excitations.

Conclusions:

Theoretical insights into the spectral characteristics of heavy-element complexes were provided.
The study validates advanced computational methods for actinyl spectral analysis.
Established a foundation for using M4,5-edge spectroscopy to probe chemical activities and bonding in heavy-element compounds.

More Related Videos

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

Published on: June 7, 2018

U2O5 Film Preparation via UO2 Deposition by Direct Current Sputtering and Successive Oxidation and Reduction with Atomic Oxygen and Atomic Hydrogen

U2O5 Film Preparation via UO2 Deposition by Direct Current Sputtering and Successive Oxidation and Reduction with Atomic Oxygen and Atomic Hydrogen

Published on: February 21, 2019

Related Concept Videos

¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)

¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)

When proton-coupled carbon-13 spectra are simplified by a broadband proton decoupling technique, structural information about the coupled protons is lost. Distortionless enhancement by polarization transfer (DEPT) is a technique that provides information on the number of hydrogens attached to each carbon in a molecule. While the DEPT experiment utilizes complex pulse sequences, the pulse delay and flip angle are specifically manipulated. The resulting signals have different phases depending on...

¹H NMR: Complex Splitting

¹H NMR: Complex Splitting

A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied...

¹H NMR: Interpreting Distorted and Overlapping Signals

¹H NMR: Interpreting Distorted and Overlapping Signals

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...

NMR Spectroscopy: Chemical Shift Overview

NMR Spectroscopy: Chemical Shift Overview

The position of the absorption signal of a sample is reported relative to the position of the signal of tetramethylsilane (TMS), which is added as an internal reference while recording spectra. The difference between the absorption frequencies of the sample and TMS (in Hz) is divided by the spectrometer operating frequency (in MHz) to obtain a dimensionless quantity called the chemical shift. It is reported on the δ (delta) scale and expressed in parts per million.
For instance, the proton...

Nuclear Overhauser Enhancement (NOE)

Nuclear Overhauser Enhancement (NOE)

Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically bonded or involved in J-coupling. This phenomenon, called the Nuclear Overhauser Enhancement (NOE), results from through-space interactions between the nuclear spins. The NOE effect decreases with increasing internuclear distance and is generally not observed beyond 4 angstroms. In NOE, dipole-dipole interactions between neighboring...

Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals

Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals

Ideally, an unpaired electron shows a single peak in the EPR spectrum due to the transition between the two spin energy states. However, coupling interactions can occur between the spins of the unpaired electron and any neighboring spin-active nuclei. This hyperfine coupling results in hyperfine splitting, where the EPR signal is split into multiplets. The signals split into 2nI + 1 peaks, where n is the number of equivalent nuclei and I is the nuclear spin. These splitting patterns provide...

Articles linked to this work by shared authors, journal, and citation graph.

Pediatric Repetitive Mild Traumatic Brain Injury Elicits T Cell-Mediated Neuroinflammation.

Neurotrauma reports·2026

Four-component relativistic density functional theory: grid requirements and small-component contributions.

Physical chemistry chemical physics : PCCP·2026

One-dimensional anionic radical chains based on M2P2 rings (M = Ti, Zr, Hf).

Chemical science·2026

Ab initio two-spinor Ehrenfest dynamics with magnetic field.

Physical chemistry chemical physics : PCCP·2026

Coupling High-Throughput Density Functional Theory, Automated Experimentation, and Adaptive Experimental Design To Achieve Selective Rare-Earth Element Separations.

Journal of the American Chemical Society·2026

One-Pot, One-Step Mn-bis(imino)pyridine Complexes through Sonochemistry.

Inorganic chemistry·2026

See all related articles