Anisotropic charge-transfer effects in the asymmetric Fe(CN)5NO octahedron of sodium nitroprusside: a soft X-ray absorption spectroscopy study

Ysuke Nanba; Daisuke Asakura; Masashi Okubo; Haoshen Zhou; Kenta Amemiya; Kozo Okada; Per-Anders Glans; Catherine A . Jenkins; Elke Arenholz; Jinghua Guo

doi:10.1039/C3CP55471F

Anisotropic charge-transfer effects in the asymmetric Fe(CN)₅NO octahedron of sodium nitroprusside: a soft X-ray absorption spectroscopy study†

Y

suke Nanba,^a Daisuke Asakura,*^a Masashi Okubo,^a Haoshen Zhou,^a Kenta Amemiya,^b Kozo Okada,^c Per-Anders Glans,^d Catherine A . Jenkins,^d Elke Arenholz^d and Jinghua Guo^d

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* Corresponding authors

^a Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568, Japan
E-mail: daisuke-asakura@aist.go.jp

^b Photon Factory, IMSS, High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305-0801, Japan

^c The Graduate School of Natural Science and Technology, Okayama University, Okayama 700-8530, Japan

^d Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

Abstract

The electronic structure of Na₂[Fe(CN)₅NO]·2H₂O (sodium nitroprusside: SNP) was investigated by using soft X-ray absorption (XA) spectroscopy. The Fe L_2,3-edge XA spectrum of SNP exhibited distinct and very large satellite peaks for L₃ and L₂ regions, which is different from the spectra of hexacyanoferrates and the other iron compounds. A configuration-interaction full-multiplet calculation, in which the ligand molecular orbitals for the C_4v symmetry were taken into account, revealed the Fe²⁺ low-spin state with very strong effects of metal-to-ligand charge-transfer from the Fe 3d to NO 2p orbitals.

Physical Chemistry Chemical Physics

Anisotropic charge-transfer effects in the asymmetric Fe(CN)₅NO octahedron of sodium nitroprusside: a soft X-ray absorption spectroscopy study†

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Anisotropic charge-transfer effects in the asymmetric Fe(CN)₅NO octahedron of sodium nitroprusside: a soft X-ray absorption spectroscopy study

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Physical Chemistry Chemical Physics