DOI: 10.1063/1.3081884. Structural analysis of ultrafast extended x-ray absorption fine structure with subpicometer spatial resolution: Application to spin crossover complexes

Structural analysis of ultrafast extended x-ray absorption fine structure with subpicometer spatial resolution: Application to spin crossover complexes

10.1063/1.3081884

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

We present a novel analysis of time-resolved extended x-ray absorption fine structure (EXAFS) spectra based on the fitting of the experimental transients obtained from optical pump/x-ray probe experiments. We apply it to the analysis of picosecond EXAFS data on aqueous [FeII(bpy)3]2+, which undergoes a light induced conversion from its low-spin (LS) ground state to the short-lived (τ≈650 ps) excited high-spin (HS) state. A series of EXAFS spectra were simulated for a collection of possible HS structures from which the ground state fit spectrum was subtracted to generate transient difference absorption (TA) spectra. These are then compared with the experimental TA spectrum using a least-squares statistical analysis to derive the structural change. This approach reduces the number of required parameters by cancellation in the differences. It also delivers a unique solution for both the fractional population and the extracted excited state structure. We thus obtain a value of the Fe–N bond elongation in the HS state with subpicometer precision (0.203±0.008 Å).

Bibliography

Gawelda, W., Pham, V.-T., van der Veen, R. M., Grolimund, D., Abela, R., Chergui, M., & Bressler, C. (2009). Structural analysis of ultrafast extended x-ray absorption fine structure with subpicometer spatial resolution: Application to spin crossover complexes. The Journal of Chemical Physics, 130(12).

Authors 7

W. Gawelda (first)
V.-T. Pham (additional)
R. M. van der Veen (additional)
D. Grolimund (additional)
R. Abela (additional)
M. Chergui (additional)
C. Bressler (additional)

References 38 Referenced 67

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Dates

Type	When
Created	16 years, 5 months ago (April 1, 2009, 10:08 a.m.)
Deposited	6 months, 4 weeks ago (Feb. 8, 2025, 3:07 p.m.)
Indexed	2 weeks ago (Aug. 23, 2025, 1:04 a.m.)
Issued	16 years, 5 months ago (March 28, 2009)
Published	16 years, 5 months ago (March 28, 2009)
Published Online	16 years, 5 months ago (March 31, 2009)
Published Print	16 years, 5 months ago (March 28, 2009)

Funders 0

None

BibTeX

@article{Gawelda_2009, title={Structural analysis of ultrafast extended x-ray absorption fine structure with subpicometer spatial resolution: Application to spin crossover complexes}, volume={130}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.3081884}, DOI={10.1063/1.3081884}, number={12}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Gawelda, W. and Pham, V.-T. and van der Veen, R. M. and Grolimund, D. and Abela, R. and Chergui, M. and Bressler, C.}, year={2009}, month=mar }

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