Towards systematically improvable models for actinides in condensed phase: the electronic spectrum of uranyl in Cs2UO2Cl4 as a test case

Literature Information

Publication Date 2013-07-12
DOI 10.1039/C3CP52090K
Impact Factor 3.676
Authors

André Severo Pereira Gomes, Christoph R. Jacob, Florent Réal, Lucas Visscher, Valérie Vallet


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Abstract

In this work we explore the use of frozen density embedding [Gomes et al., Phys. Chem. Chem. Phys., 2008, 10, 5353] as a way to construct models of increasing sophistication for describing the low-lying electronic absorption spectra of UO22+ in the Cs2UO2Cl4 crystal. We find that a relatively simple embedding model, in which all but the UO22+ unit are represented by an embedding potential, can already describe the main spectral features and the main environment effects can be attributed to the four chloride ions situated at the UO22+ equatorial plane. Contributions from species further away, albeit small, are found to be important for reaching a close agreement with experimentally observed quantities such as the excited states' relative positions. These findings suggest that such an embedding approach is a viable alternative to supermolecular calculations employing larger models of actinyl species in condensed phase. Nevertheless, we observe a slight red shift of the excitation energies calculated with our models compared to experimental results, and attribute this discrepancy to inaccuracies in the underlying structural parameters.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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