H. Vereammen et al., Optical transitions of Rh2+ in NaCl crystals studied by electron spin resonance and magnetic circular dichroism, PHYS REV B, 59(17), 1999, pp. 11286-11292
Electron spin resonance, magnetic circular dichroism, and optical absorptio
n spectra of a paramagnetic Rh2+ complex are investigated in Rh3+ doped sol
ution-grown NaCl single crystals, x irradiation of the crystals at 77 K fol
lowed by a warm-up to room temperature results in the formation of a stable
low-spin Jahn-Teller distorted RhCl64- complex possessing D-4h symmetry. T
he unpaired electron is largely localized in the 4d(z2) orbital of the Rh2(4d(7)) which is involved in a sigma type molecular bond with two symmetric
ally placed Cl- ions along [001]. The magnetic circular dichroism and optic
al absorption measurements at 1.4 K reveal two main bands around 12 200 cm(
-1) and 16 200 cm(-1). Within the octahedral Tanabe-Sugano formalism of the
Rh2+ these two absorptions are associated with two vibronically allowed E-
2(g)-->T-2(1g),T-2(2g) molecular transitions. This assignment is in quantit
ative agreement with the analysis of the g matrix components. A small MCD f
eature at 15 200 cm(-1) is tentatively associated with two coinciding E-2(g
)-->T-2(1g),T-2(2g) transitions of another, probably a ligand-exchanged, Rh
2+ center. [S0163-1829(99)00517-2].