Electronic structure studies of bismuth compounds using high energy resolution X-ray spectroscopy and ab initio calculations

Uncovering the Origin of the Emitting States in Bi3+-Activated CaMO3 (M = Zr, Sn, Ti) Perovskites: Metal-To-Metal Charge Transfer Versus s–p Transitions

“…Relative shifts of the absorption edge are often correlated to a change in the valence state of the absorber; however, chemical and structural effects are deeply interconnected in XANES, and not always this correlation can be made. In the case of Bi, the L 3 edge is very sensitive to the local structure, whereas in the L 1 edge a systematic shift in accord with the valence-state change is found . The features after the postedge differ from both references and are related to the local structure of Bi dopants.…”

“…In the case of Bi, the L 3 edge is very sensitive to the local structure, whereas in the L 1 edge a systematic shift in accord with the valence-state change is found. 77 The features after the postedge differ from both references and are related to the local structure of Bi dopants.…”

“…Black dots and red squares represent the emission energy from the 3 P 1 and MMCT states, respectively. significantly differ among different Bi-based compounds in terms of energy shift and spectral shapes, 77 being sensitive not only to the oxidation state but also to both the ligand environment and the crystal structure. By considering the different nature of the emitting transitions of Bi 3+ in CaZrO 3 and CaSnO 3 , XANES analysis was carried out to investigate the local Bi environment.…”

“…Recently, Mistonov et al demonstrated the clear advantage of measuring XANES in the high-energy resolution mode compared to the traditional total fluorescence mode to investigate bismuth-based compounds such as metallic Bi, Bi 2 O 3 , BiPO 4 , Bi 4 (GeO 4 ) 3 , and NaBiO 3 . In addition, the profiles of the Bi L 3 -edge spectra were demonstrated to significantly differ among different Bi-based compounds in terms of energy shift and spectral shapes, being sensitive not only to the oxidation state but also to both the ligand environment and the crystal structure. By considering the different nature of the emitting transitions of Bi 3+ in CaZrO 3 and CaSnO 3 , XANES analysis was carried out to investigate the local Bi environment.…”

Synchrotron X‐ray Spectroscopic Investigations of In‐Situ‐Formed Alloy Anodes for Magnesium Batteries

“…The Bi L3 is used to probe 6s and 5d electrons, due to the excitation of 2p3/2 electron to unfilled s or d orbitals. [ 37 ] The decreasing peak intensity of Bi L3 from the d_0.20 to d_0.05 states demonstrates an increasing electron density of Bi during the alloying process while the electron density decreased when charged back to 1.0 V (Figure 4e). In addition, compared with the XPS spectrum of pristine BS‐Bi, the electrode at the state of d_0.05 V exhibits strong Mg 2s and Mg KLL Auger peaks, suggesting integration of Mg in BS‐Bi electrode to form a Mg–Bi alloy phase (Figures S22 and S23, Supporting Information).…”