Magneto-Optical Investigation of the Broad Spin-Allowed Bands in the Metal-Metal-Bonded Complexes Mo2X93− (X = Cl, Br)x

Stranger R., Moran G., Krausz E. and Medley G. (1993) Magneto-Optical Investigation of the Broad Spin-Allowed Bands in the Metal-Metal-Bonded Complexes Mo2X93− (X = Cl, Br)x. Inorganic Chemistry, 32 21: 4555-4560. doi:10.1021/ic00073a015


Author Stranger R.
Moran G.
Krausz E.
Medley G.
Title Magneto-Optical Investigation of the Broad Spin-Allowed Bands in the Metal-Metal-Bonded Complexes Mo2X93− (X = Cl, Br)x
Journal name Inorganic Chemistry   Check publisher's open access policy
ISSN 1520-510X
Publication date 1993-01-01
Sub-type Article (original research)
DOI 10.1021/ic00073a015
Open Access Status Not yet assessed
Volume 32
Issue 21
Start page 4555
End page 4560
Total pages 6
Language eng
Subject 1606 Physical and Theoretical Chemistry
1604 Inorganic Chemistry
Abstract The broad spin-allowed bands observed between 16 000 and 25 000 cm in CsMoX (X = Cl, Br) have been investigated by low-temperature single-crystal absorption and MCD spectroscopy. Using the exchange-coupled pair model, it is shown that these bands can be assigned to singly-excited pair states which involve trigonal t → e single-ion excitation. Weaker, sharper features are also observed which are attributed to doubly-excited pair states arising from intraconfigurational transitions (spin-flips) within the t single-ion orbitals. The spectral features are successfully modeled as a function of the Racah B and C parameters, the splitting between the trigonal t and e single-ion orbitals, and the metal-metal π exchange interaction. From the analysis, the metal-metal π interaction in the bromide complex is shown to be weaker than that of the chloride complex. Spin-polarized, transition-state calculations using the SCF-Xα-SW method were carried out on CsMoCl. Although the spin-singlet σ(Mo) → σ*(Mo) transition is calculated around 21 000 cm and is electric-dipole allowed, the low intensity (ϵ < 130) in this region indicates that this transition lies to higher energy, above 27 000 cm.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import - Archived
 
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