5f covalency in [U(CH)] was probed with carbon K-edge X-ray absorption spectroscopy (XAS) and electronic structure theory. The results revealed U 5f orbital participation in δ-bonding in both the ground- and core-excited states; additional 5f ϕ-mixing is observed in the core-excited states. Comparisons with U(CH) show greater δ-covalency for [U(CH)].
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http://dx.doi.org/10.1039/d1cc03414f | DOI Listing |
J Phys Chem A
December 2024
Centre for Computational Chemistry, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, United Kingdom.
First-principles simulations of excited-state X-ray spectra are becoming increasingly important to interpret the wealth of electronic and geometric information contained within femtosecond X-ray absorption spectra recorded at X-ray Free Electron Lasers (X-FELs). However, because the transition dipole matrix elements must be calculated between two excited states (i.e.
View Article and Find Full Text PDFJ Phys Chem A
November 2024
Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen Ø DK 2100, Denmark.
The development of accurate and fast computational procedures for the calculation of X-ray spectroscopies is paramount to facilitate theoretical analysis of modern X-ray experiments on molecules. Herein, we present the extension of Cluster Perturbation theory to comprehend the calculation of core excited states and core ionization potentials using the core-valence separation approximation, which has seen widespread success for various quantum chemistry methods. We derive the theoretical framework for introducing core-valence separation into Cluster Perturbation series for excitation energies and display the performance of the methodology in S(D) orbital excitation spaces.
View Article and Find Full Text PDFJ Phys Chem A
November 2024
Chair of Theoretical Chemistry, Department of Chemistry, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, Munich D-81377, Germany.
J Chem Phys
October 2024
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA.
Electron attachment to pyridine results in electronic resonances, metastable states that can decay through electronic or nuclear degrees of freedom. This study uses orbital stabilization techniques combined with bound electronic structure methods, based on equation of motion coupled cluster or multi-reference methods, to calculate positions and widths of electronic resonances in pyridine that exist below 10 eV. We report four 2B1 and four 2A2 resonances, including one 2B1 not previously reported experimentally and two 2A2 resonances not reported at all in the literature.
View Article and Find Full Text PDFJ Phys Chem A
October 2024
Department of Chemistry, University of California, Berkeley, California 94720, United States.
A coherent vibrational wavepacket is launched and manipulated in the symmetric stretch (a) mode of CBr, by impulsive stimulated Raman scattering (ISRS) from nonresonant 400 nm laser pump pulses with various peak intensities on the order of tens of 10 W/cm. Extreme ultraviolet (XUV) attosecond transient absorption spectroscopy (ATAS) records the wavepacket dynamics as temporal oscillations in XUV absorption energy at the bromine M 3d edges around 70 eV. The results are augmented by nuclear time-dependent Schrödinger equation simulations.
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