Solvation dynamics monitored by combined X-ray spectroscopies and scattering: photoinduced spin transition in aqueous [Fe(bpy)3]2+

被引：17

作者：

Bressler, C. ^{[1
,2
]}

Gawelda, W. ^{[1
]}

Galler, A. ^{[1
]}

Nielsen, M. M. ^{[3
]}

Sundstrom, V. ^{[4
]}

Doumy, G. ^{[5
]}

March, A. M. ^{[5
]}

Southworth, S. H. ^{[5
]}

Young, L. ^{[6
]}

Vanko, G. ^{[6
]}

机构：

[1] European XFEL, D-22761 Hamburg, Germany

[2] Hamburg Ctr Ultrafast Imaging, D-22761 Hamburg, Germany

[3] Tech Univ Denmark, Dept Phys, Ctr Mol Movies, DK-2800 Lyngby, Denmark

[4] Lund Univ, Dept Chem Phys, S-22100 Lund, Sweden

[5] Argonne Natl Lab, Argonne, IL 60439 USA

[6] Hungarian Acad Sci, Wigner Res Ctr Phys, H-1525 Budapest, Hungary

来源：

FARADAY DISCUSSIONS | 2014年 / 171卷

基金：

新加坡国家研究基金会; 欧洲研究理事会;

关键词：

ABSORPTION SPECTROSCOPY; MOLECULAR-STRUCTURES; CROSSOVER DYNAMICS; STATE; COMPLEXES; LIQUIDS; SOLVENT; XANES;

D O I：

10.1039/c4fd00097h

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：

We have studied the photoinduced low spin (LS) to high spin (HS) conversion of aqueous Fe(bpy)(3) with pulse-limited time resolution. In a combined setup permitting simultaneous X-ray diffuse scattering (XDS) and spectroscopic measurements at a MHz repetition rate we have unraveled the interplay between intramolecular dynamics and the intermolecular caging solvent response with 100 ps time resolution. On this time scale the ultrafast spin transition including intramolecular geometric structure changes as well as the concomitant bulk solvent heating process due to energy dissipation from the excited HS molecule are long completed. The heating is nevertheless observed to further increase due to the excess energy between HS and LS states released on a subnanosecond time scale. The analysis of the spectroscopic data allows precise determination of the excited population which efficiently reduces the number of free parameters in the XDS analysis, and both combined permit extraction of information about the structural dynamics of the first solvation shell.

引用

页码：169 / 178

页数：10

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