Tetrahedral Iron in the Active Center of Plant Ferredoxins and Beef Adrenodoxin*
Title: Stimulated X-ray Raman and Absorption Spectroscopy of Iron–Sulfur Dimers
Abstract
Iron–sulfur complexes play an important role in biological processes such as metabolic electron transport. A detailed understanding of the mechanism of long-range electron transfer requires knowledge of the electronic structure of the complexes, which has traditionally been challenging to obtain, either by theory or by experiment, but the situation has begun to change with advances in quantum chemical methods and intense free electron laser light sources. We compute the spectra for stimulated X-ray Raman spectroscopy (SXRS) and absorption spectroscopy of homovalent and mixed-valence [2Fe–2S] complexes, using the ab initio density matrix renormalization group algorithm. The simulated spectra show clear signatures of the theoretically predicted dense low-lying excited states within the d–d manifold. Finally, the difference in spectral intensity between the absorption-active and Raman-active states provides a potential mechanism to selectively excite states by a proper tuning of the excitation pump, to access the electronic dynamics within this manifold.
- Authors:
-
[1]; [1]; [1]; [3]
- Univ. of California, Irvine, CA (United States)
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- California Institute of Technology (CalTech), Pasadena, CA (United States); Beijing Normal University (China)
- Publication Date:
- Research Org.:
- Univ. of California, Irvine, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1800157
- Grant/Contract Number:
- FG02-04ER15571
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 21; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Science & Technology; Materials Science; Physics; Oligomers; Electrical properties; Energy; Phase transitions; Excited states
Citation Formats
Cho, Daeheum, Rouxel, Jeremy R., Mukamel, Shaul, Kin-Lic Chan, Garnet, and Li, Zhendong. Stimulated X-ray Raman and Absorption Spectroscopy of Iron–Sulfur Dimers. United States: N. p., 2019. Web. doi:10.1021/acs.jpclett.9b02414.
Cho, Daeheum, Rouxel, Jeremy R., Mukamel, Shaul, Kin-Lic Chan, Garnet, & Li, Zhendong. Stimulated X-ray Raman and Absorption Spectroscopy of Iron–Sulfur Dimers. United States. https://doi.org/10.1021/acs.jpclett.9b02414
Cho, Daeheum, Rouxel, Jeremy R., Mukamel, Shaul, Kin-Lic Chan, Garnet, and Li, Zhendong. 2019. "Stimulated X-ray Raman and Absorption Spectroscopy of Iron–Sulfur Dimers". United States. https://doi.org/10.1021/acs.jpclett.9b02414. https://www.osti.gov/servlets/purl/1800157.
@article{osti_1800157,
title = {Stimulated X-ray Raman and Absorption Spectroscopy of Iron–Sulfur Dimers},
author = {Cho, Daeheum and Rouxel, Jeremy R. and Mukamel, Shaul and Kin-Lic Chan, Garnet and Li, Zhendong},
abstractNote = {Iron–sulfur complexes play an important role in biological processes such as metabolic electron transport. A detailed understanding of the mechanism of long-range electron transfer requires knowledge of the electronic structure of the complexes, which has traditionally been challenging to obtain, either by theory or by experiment, but the situation has begun to change with advances in quantum chemical methods and intense free electron laser light sources. We compute the spectra for stimulated X-ray Raman spectroscopy (SXRS) and absorption spectroscopy of homovalent and mixed-valence [2Fe–2S] complexes, using the ab initio density matrix renormalization group algorithm. The simulated spectra show clear signatures of the theoretically predicted dense low-lying excited states within the d–d manifold. Finally, the difference in spectral intensity between the absorption-active and Raman-active states provides a potential mechanism to selectively excite states by a proper tuning of the excitation pump, to access the electronic dynamics within this manifold.},
doi = {10.1021/acs.jpclett.9b02414},
url = {https://www.osti.gov/biblio/1800157}, journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = 21,
volume = 10,
place = {United States},
year = {Wed Sep 18 00:00:00 EDT 2019},
month = {Wed Sep 18 00:00:00 EDT 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Works referenced in this record:
Propagation of a strong x-ray pulse: Pulse compression, stimulated Raman scattering, amplified spontaneous emission, lasing without inversion, and four-wave mixing
journal, January 2010
- Sun, Yu-Ping; Liu, Ji-Cai; Wang, Chuan-Kui
- Physical Review A, Vol. 81, Issue 1
The two-iron ferredoxins in spinach, parsley, pig adrenal cortex, Azotobacter vinelandii, and Clostridium pasteurianum: Studies by magnetic field Mössbauer spectroscopy
journal, November 1971
- Dunham, W. R.; Bearden, Alan J.; Salmeen, I. T.
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Source: https://www.osti.gov/biblio/1800157-stimulated-ray-raman-absorption-spectroscopy-ironsulfur-dimers
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