Studies of the EPR g factor for Ni2+ ion in CsMgX3 (X=Cl, Br, I) crystals.
The complete high-order perturbation formula of g factor, including not only the widely used crystal-field (CF) mechanism, but also the neglected change-transfer (CT) mechanism in the CF theory, is established for a 3d8 ion in cubic octahedral site. From the formula, the g-shifts Deltag (=g-gs, where gs approximately 2.0023, the value of free electron) of Ni2+ ion in CsMgX3 (X=Cl, Br, I) crystals are calculated. The results suggest that the g-shift DeltagCT due to the CT mechanism and the DeltagCF due to CF mechanism have the same sign and the importance of DeltagCT follows the order: CsMgI3: Ni2+>CsMgBr3: Ni2+>CsMgCl3: Ni2+. So, in the calculations of g or Deltag of 3dn MXm clusters in crystals, the contributions to g factor from both the CT and CF mechanisms should be taken into account in the case of heavy-element ligand ions, such as Br- and I- ions.
Zheng
Wen-Chen
WC
Department of Material Science, Sichuan University, Chengdu 610064, People's Republic of China. zhengwc1@163.com
Wu
Xiao-Xuan
XX
D001965:Bromides / Q000737:chemistry*; D002413:Cations, Divalent / Q000737:chemistry; D002586:Cesium / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D003460:Crystallization; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods; D007454:Iodides / Q000737:chemistry*; D015636:Magnesium Chloride / Q000737:chemistry*; D017616:Magnesium Compounds / Q000737:chemistry*; D009532:Nickel / Q000737:chemistry*
D001965:Bromides; D002413:Cations, Divalent; D002712:Chlorides; D007454:Iodides; D017616:Magnesium Compounds; D015636:Magnesium Chloride; C078556:cesium bromide; D002586:Cesium; D009532:Nickel; C028019:cesium chloride; C040050:cesium iodide; C510205:magnesium iodide