Electronic Structure of Hemin in Solution Studied by Resonant X-ray Emission Spectroscopy and Electronic Structure Calculations

被引：18

作者：

Atak, Kaan ^{[1
,2
]}

Golnak, Ronny ^{[1
,3
]}

Xiao, Jie ^{[1
]}

Suljoti, Edlira ^{[1
]}

Pflueger, Mika ^{[1
,2
]}

Brandenburg, Tim ^{[1
,2
]}

Winter, Bernd ^{[1
]}

Aziz, Emad F. ^{[1
,2
]}

机构：

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

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

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

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2014年 / 118卷 / 33期

基金：

欧洲研究理事会;

关键词：

APPROXIMATE COULOMB POTENTIALS; AUXILIARY BASIS-SETS; COORDINATION; COMPLEXES; EXCHANGE; WATER; IRON; RN;

D O I：

10.1021/jp505129m

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：

Resonant inelastic X-ray scattering spectra at the iron L-edge from hemin in dimethyl sulfoxide liquid solution are reported. Our experiments, which are interpreted with the help of electronic structure calculations, support earlier assignments of hemin solvent interactions, including the iron spin state and the role of the chloride ligand obtained from a total fluorescence yield study. The analysis of the explicit radiative relaxation channels of 2p core-level excited iron, explored in the present work, allows for a rather quantitative assignment of the orbitals involved in the excitation - deexcitation process of the core-excited hemin in solution. We specifically distinguish between contributions of partially and fully occupied valence orbitals to the broad X-ray emission band. In addition, our calculations reveal a detailed picture of the character of these orbitals.

引用

页码：9938 / 9943

页数：6

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