Local Energy Gap Opening Induced by Hemin Dimerization in Aqueous Solution

被引：16

作者：

Golnak, Ronny ^{[1
,2
]}

Xiao, Jie ^{[1
]}

Atak, Kaan ^{[1
,3
]}

Khan, Munirah ^{[1
,3
]}

Suljoti, Edlira ^{[1
]}

Aziz, Emad F. ^{[1
,3
,4
]}

机构：

[1] Helmholtz Zentrum Berlin Mat & Energie, Inst Methods Mat Dev, Joint Ultrafast Dynam Lab Solut & Interfaces JULi, D-12489 Berlin, Germany

[2] Free Univ Berlin, Fachbereich Chem, D-14195 Berlin, Germany

[3] Free Univ Berlin, Fachbereich Phys, D-14195 Berlin, Germany

[4] Natl Inst Nat Sci, Inst Mol Sci, Okazaki, Aichi 4448585, Japan

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2015年 / 119卷 / 07期

基金：

欧洲研究理事会;

关键词：

RAY-ABSORPTION SPECTROSCOPY; PARTIAL FLUORESCENCE YIELD; ELECTRONIC-STRUCTURE; L-EDGE; IRON; METALATION; PORPHYRINS; MOLECULES; CHEMISTRY; EMISSION;

D O I：

10.1021/jp509966q

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The local electronic structure of the hemin Fe center has been investigated by X-ray absorption and emission spectroscopy (XAS/XES) for hemin in aqueous solution where hemin dimerization occurs. The XAS and XES spectra of the hemin dimer were then compared with those of the hemin monomer we previously studied in dimethyl sulfoxide solution. A local energy gap opening at the Fe sites was observed for the hemin dimer, with the occupied valence states shifted to lower binding energies, while the unoccupied valence states share the same energies as the hemin monomer. Such a gap opening is argued to originate from the Fe 3d orbital localization induced by hemin dimerization in aqueous solution.

引用

页码：3058 / 3062

页数：5

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