Mixed Valence Compounds: Temperature variation of the intervalence absorption band of hexachloroantimonate(III, V) ions in a crystal lattice

Kosmas Prassides, Peter Day

研究成果: Chapter

抄録

The bandshape of the intervalence absorption of SbC16 3- and SbCl6 -, has been measured from 300 to 4 K in a crystal of (CH3NH3) 2SbxSn1-x, C16 in order to study the variation of the zeroth, first and second moments. At all temperatures the bandshape is Gaussian, as required by the vibronic model of Piepho, Krausz and Schatz (P.K.S.) in the weak-interaction limit. From the temperature dependence of the second moment, we estimate the electronphonon coupling constant (and hence the displacement in vibrational coordinate from the ground state to the intervalence charge-transfer state), together with the effective phonon frequency coupled to the transition. The latter is very close to the mean of the ground-state totally symmetric Sb-Cl strtching modes of SbCl6 3- and SbCl6 - and the displacement in vibrational coordinate is also about half the difference between the Sb-Cl crystallographic bond lengths in the two complex ions. To explain the temperature dependence of the zeroth and first moments anharmonicity must be involved. A simple model for the variation of intervalence excitation energy with interionic distance, combined with an isotropic model of the thermal lattice expansion, gives a quantitative account of the change in first moment with temperature and a qualitative description of the change in zeroth moment.

本文言語English
ホスト出版物のタイトルMolecules into Materials
ホスト出版物のサブタイトルCase Studies in Materials Chemistry-Mixed Valency, Magnetism and Super Conductivity
出版社World Scientific Publishing Co.
ページ389-399
ページ数11
ISBN(電子版)9789812706836
ISBN(印刷版)9812700382, 9789812700384
DOI
出版ステータスPublished - 2007 1月 1

ASJC Scopus subject areas

  • 化学 (全般)
  • 工学(全般)
  • 材料科学(全般)
  • 物理学および天文学(全般)

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