Evaluation of electronic state of Cs-adsorbed clay minerals by NEXAFS analysis using DFT calculations

Suzuki, Chikashi; Yaita, Tsuyoshi; Suzuki, Shinichi; Pacold, J.*; Altman, A. B.*; Minasian, S. G.*; Tyliszczak, T.*; Shuk, D. K.*; Yoshida, Hiroyuki; Osaka, Masahiko

Journal of Physics and Chemistry of Solids, 127, p.169 - 177, 2019/04

https://doi.org/10.1016/j.jpcs.2018.11.011

A combined method of NEXAFS measurement and DFT-calculation was employed for Cs evaluation in clay minerals. The Cs M NEXAFS spectra of Cs halides were analyzed using the DFT-calculations, and were well reproduced by incorporating the core-hole strength. The Cs M NEXAFS spectrum of clay minerals was well-reproduced by the DFT-calculations including the major transitions and tail structures with the established method. The further evaluation of this spectrum by charge density suggests that these major transitions and the tail structures likely reflect bonding states and local environments around the Cs atoms. Comparison of electronic states of Cs in the clay mineral with those in the Cs halides by DFT-calculations has shown that the interaction between Cs and the nearest-neighbor atom is largest in the clay mineral, because the energy level of Cs-5s and 5p is closer to that of O-2s and 2p than the s and p orbitals of other alkali metal and alkali earth metal elements.