SOFT X-RAY ABSORPTION SPECTRA OF THE LITHIUM PHTHALOCYANINE RADICAL

Toshihiro Okajima, Hitoshi Fujimoto, Michinori Sumitomo, Tohro Araki, Eisuke Ito, Hisao Ishii, Yukio Ouchi and Kazuhiko Seki
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Toshihiro Okajima: Japan Synchrotron Radiation Research Insitute, 1-1-1 Kouto, Mikazuki-cho, Sayo-gun, Hyogo 679-5198, Japan
Hitoshi Fujimoto: Department of Chemistry, Kumamoto University, 2-93-1 Kurokami, Kumamoto 860-8555, Japan
Michinori Sumitomo: Department of Chemistry, Kumamoto University, 2-93-1 Kurokami, Kumamoto 860-8555, Japan
Tohro Araki: Department of Chemistry, Saitama University, 255 Shimoohkubo, Saitama, Saitama 338-8570, Japan
Eisuke Ito: Frontier Research System, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
Hisao Ishii: Department of Chemistry, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan
Yukio Ouchi: Department of Chemistry, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan
Kazuhiko Seki: Department of Chemistry, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan

Surface Review and Letters (SRL), 2002, vol. 09, issue 01, 441-446

Abstract: In near edge X-ray absorption fine structure (NEXAFS) spectra of carbon (C) and nitrogen (N) K-edge regions were measured for the stable radical compound lithium phthalocyanine (LiPc). The observed spectra were compared with those of metal free Pc(H2Pc), copper Pc (CuPc), and zinc Pc (ZnPc). The spectral features in the C K-edge region of LiPc were different from those of other Pcs in the low photon energy region. An additional peak around 283.5 eV was observed only in the spectrum of LiPc. On the other hand, the spectral features of these MPcs in the N K-edge region were similar and did not show a corresponding extra peak. These results were explained by the patterns of molecular orbitals of these Pcs and the selection rules of X-ray absorption in the localized core-hole picture. The extra peak observed in the C K-edge region is assigned to the excitation from C1s to the highest occupied molecular orbital (HOMO), which is only singly occupied due to the radical nature of the phthalocyanine ring. Group-theoretical consideration indicated that the transition from N1s to the HOMO is not allowed, and this explains the lack of an extra peak at the N K-edge.

Date: 2002
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DOI: 10.1142/S0218625X0200252X

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