Effect of electron correlation in the decomposition of core level binding energy shifts into initial and final state contributions

Literature Information

Publication Date 2019-04-12
DOI 10.1039/C9CP01569H
Impact Factor 3.676
Authors

Marc Figueras, Carmen Sousa, Francesc Illas


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Abstract

The influence of electron correlation into the decomposition of core level binding energy shifts, measured by X-ray photoelectron spectroscopy (XPS), into initial and final effects is analysed for a series of molecules where these effects are noticeable. Moreover, the series of molecules is chosen in such a way that electron delocalization and increasing number of electrons may provide a large screening of the core hole. A detailed analysis shows that the Hartree–Fock decomposition is biased whereas a physically meaningful decomposition is obtained when electron correlation effects are taken into account. The results show that in this case, trends in core level binding energy shifts are driven by initial state effects thus providing further support to the use of these observable quantities to interpret changes in the chemical bond in the neutral molecule rather than on the core ionized cation. Consequences for the theoretical interpretation of XPS data in materials and surface science are discussed.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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