TY - JOUR
T1 - Identification of Second Shell Coordination in Transition Metal Species Using Theoretical XANES
T2 - Example of Ti-O-(C, Si, Ge) Complexes
AU - Spanjers, Charles S.
AU - Guillo, Pascal
AU - Tilley, T. Don
AU - Janik, Michael J.
AU - Rioux, Robert M.
N1 - Funding Information:
C.S.S. and R.M.R. acknowledge the Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Sciences Program under Grant No. DE-FG02-12ER16364 for funding of this research. R.M.R. acknowledges the financial support of 3M through a Nontenured Faculty Grant. C.S.S. acknowledges the National Science Foundation under Grant No. DGE1255832. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. Beamline X19A is supported, in part, by US DOE Grant No. DE-FG02-05ER15688. The authors thank Nebojsa Marinkovic for help with XAS measurements.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2017/1/12
Y1 - 2017/1/12
N2 - X-ray absorption near-edge structure (XANES) is a common technique for elucidating oxidation state and first shell coordination geometry in transition metal complexes, among many other materials. However, the structural information obtained from XANES is often limited to the first coordination sphere. In this study, we show how XANES can be used to differentiate between C, Si, and Ge in the second coordination shell of Ti-O-(C, Si, Ge) molecular complexes based on differences in their Ti K-edge XANES spectra. Experimental spectra were compared with theoretical spectra calculated using density functional theory structural optimization and ab initio XANES calculations. The unique features for second shell C, Si, and Ge present in the Ti K pre-edge XANES are attributed to the interaction between the Ti center and the O-X (X = C, Si, or Ge) antibonding orbitals.
AB - X-ray absorption near-edge structure (XANES) is a common technique for elucidating oxidation state and first shell coordination geometry in transition metal complexes, among many other materials. However, the structural information obtained from XANES is often limited to the first coordination sphere. In this study, we show how XANES can be used to differentiate between C, Si, and Ge in the second coordination shell of Ti-O-(C, Si, Ge) molecular complexes based on differences in their Ti K-edge XANES spectra. Experimental spectra were compared with theoretical spectra calculated using density functional theory structural optimization and ab initio XANES calculations. The unique features for second shell C, Si, and Ge present in the Ti K pre-edge XANES are attributed to the interaction between the Ti center and the O-X (X = C, Si, or Ge) antibonding orbitals.
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U2 - 10.1021/acs.jpca.6b12197
DO - 10.1021/acs.jpca.6b12197
M3 - Article
C2 - 27951643
AN - SCOPUS:85020205197
SN - 1089-5639
VL - 121
SP - 162
EP - 167
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 1
ER -