Magnetic Circular Dichroism of [Fe(CN)<SUB>6</SUB>]<SUP>3−</SUP>
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概要
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Magnetic circular dichroism (MGD) of [Fe(CN)<SUB>6</SUB>]<SUP>3−</SUP> was measured in aqueous solution and in a polyvinylalcohol film. The use of the polyvinylalcohol (PVA) film made it possible to measure the MCD and the absorption spectrum of an electrolyte such as K<SUB>3</SUB>[Fe(CN)<SUB>6</SUB>] at dry ice - methanol and liquid nitrogen temperatures, since the film was still optically transparent at lower temperatures. From a comparison between the observations at 300°K, 195°K and 77°K, the magnitude of an angular momentum due to the orbital motion of a hole in the ground state <SUP>2</SUP><I>T</I><SUB>2<I>g</I></SUB> (<I>t</I><SUB>2<I>g</I></SUB><SUP>5</SUP>) was calculated to be 0.04–0.07 Bohr magneton (β). The observed reduction of the angular momentum was interpreted to be due to partial quenching of the orbital motion by the Jahn-Teller distortion, and also to the delocalization effect between the iron <I>d</I>π orbital and the antibonding π molecular orbitals of the coordinating CN<SUP>−</SUP> ions. The B term in [Fe(CN)<SUB>6</SUB>]<SUP>3−</SUP>, which had been ignored, was predicted to be non-zero and was estimated as −2.4×10<SUP>−3</SUP> β/cm<SUP>−1</SUP> at the band I and 0.97×10<SUP>−3</SUP> β/cm<SUP>−1</SUP> at the band II.
- 公益社団法人 日本化学会の論文
著者
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Kaizu Youkoh
Department Of Chemistry Faculty Of Science Tokyo Intitute Of Technology
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Kobayashi Hiroshi
Department Of Applied Physics School Of Science And Engineering Waseda University
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Shimizu Masayuki
Department of Chemistry, Tokyo Institute of Technology
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