Ligand field effect on the chemical shift in XANES spectra of Cu(II) compounds

文献信息

发布日期 2001-02-06
DOI 10.1039/B007276L
影响因子 3.676
作者

Ken-ichi Shimizu, Hajime Maeshima, Hisao Yoshida, Atsushi Satsuma, Tadashi Hattori


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摘要

X-Ray absorption near-edge structure (XANES) spectra at the Cu L and K edges have been measured for a series of Cu(II) compounds to clarify the factor affecting the chemical shift in the XANES spectra. The energy positions of the 2p1/2 → 3d and 2p3/2 → 3d transition peaks in the Cu L2,3 XANES spectra and the 1s → 3d transition peak (pre-edge peak) in the Cu K-edge XANES spectra were strongly influenced by the chemical states of the Cu(II), i.e., the coordination geometries (tetrahedral, octahedral and square planar) and ligand electronegativity. In all the spectra, the peak position shifted to higher energy in the order of the spectrochemical series, and the shifts are explained in terms of the change in the ligand field splitting. It is proposed that chemical shifts in the 2p → 3d and 1s → 3d transitions can be attributed primarily to changes in the position of the unfilled Cu 3d level. The result demonstrates that chemical shifts in XANES spectra of Cu(II) compounds can be understood in terms of ligand field theory.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 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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