Structures and stability of AnO4 isomers, An = Pu, Am, and Cm: a relativistic density functional study

Literature Information

Publication Date 2014-03-26
DOI 10.1039/C4CP00235K
Impact Factor 3.676
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Abstract

Equilibrium structures and energetics of various isomers of molecules with stoichiometry An·4O (An = Pu, Am, and Cm) are studied through electronic structure calculations at the relativistic density functional theory level in the frame of an accurate small-core pseudopotential model. In all cases, the global minima of the An·4O potential energy surfaces correspond to dioxo-superoxido-like species, [AnO2](O2). The stability of the “true” oxides AnO4 decreases from Pu to Cm, whereas the isomers with two O2 groups become relatively more stable. Correlation between the formal oxidation states and the Bader net charges of actinide atoms is discussed. Structural parameters, vibrational frequencies and charge and spin magnetization density distributions are analyzed in order to characterize the different isomers in chemical terms. Decrease of the An oxidation states along the An series is evident.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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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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