TY - JOUR
T1 - Improved charge transfer multiplet method to simulate M- and L-edge X-ray absorption spectra of metal-centered excited states
AU - Zhang, Kaili
AU - Girolami, Gregory S.
AU - Vura-Weis, Josh
N1 - Publisher Copyright:
© International Union of Crystallography, 2018
PY - 2018/9
Y1 - 2018/9
N2 - Charge transfer multiplet (CTM) theory is a computationally undemanding and highly mature method for simulating the soft X-ray spectra of first-row transition metal complexes. However, CTM theory has seldom been applied to the simulation of excited-state spectra. In this article, the CTM4XAS software package is extended to simulate M2,3- and L2,3-edge spectra for the excited states of first-row transition metals and also interpret CTM eigenfunctions in terms of Russell–Saunders term symbols. These new programs are used to reinterpret the recently reported excited-state M2,3-edge difference spectra of photogenerated ferrocenium cations and to propose alternative assignments for the electronic state of these cations responsible for the spectroscopic features. These new programs were also used to model the L2,3-edge spectra of FeII compounds during nuclear relaxation following photoinduced spin crossover and to propose spectroscopic signatures for their vibrationally hot states.
AB - Charge transfer multiplet (CTM) theory is a computationally undemanding and highly mature method for simulating the soft X-ray spectra of first-row transition metal complexes. However, CTM theory has seldom been applied to the simulation of excited-state spectra. In this article, the CTM4XAS software package is extended to simulate M2,3- and L2,3-edge spectra for the excited states of first-row transition metals and also interpret CTM eigenfunctions in terms of Russell–Saunders term symbols. These new programs are used to reinterpret the recently reported excited-state M2,3-edge difference spectra of photogenerated ferrocenium cations and to propose alternative assignments for the electronic state of these cations responsible for the spectroscopic features. These new programs were also used to model the L2,3-edge spectra of FeII compounds during nuclear relaxation following photoinduced spin crossover and to propose spectroscopic signatures for their vibrationally hot states.
KW - X-ray spectroscopy
KW - electronic structure
KW - multiplet simulations
KW - valence excited states
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U2 - 10.1107/S1600577518009517
DO - 10.1107/S1600577518009517
M3 - Article
C2 - 30179201
AN - SCOPUS:85053012107
SN - 0909-0495
VL - 25
SP - 1600
EP - 1608
JO - Journal of Synchrotron Radiation
JF - Journal of Synchrotron Radiation
IS - 5
ER -