TY - JOUR
T1 - Stimulated X-ray Raman and Absorption Spectroscopy of Iron-Sulfur Dimers
AU - Cho, Daeheum
AU - Rouxel, Jeremy R.
AU - Mukamel, Shaul
AU - Kin-Lic Chan, Garnet
AU - Li, Zhendong
N1 - Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/11/7
Y1 - 2019/11/7
N2 - 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. Furthermore, 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.
AB - 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. Furthermore, 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.
UR - http://www.scopus.com/inward/record.url?scp=85073828231&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.9b02414
DO - 10.1021/acs.jpclett.9b02414
M3 - Article
C2 - 31532691
AN - SCOPUS:85073828231
SN - 1948-7185
VL - 10
SP - 6664
EP - 6671
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 21
ER -