Identification of Second Shell Coordination in Transition Metal Species Using Theoretical XANES: Example of Ti–O–(C, Si, Ge) Complexes
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.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- SC0012704
- OSTI ID:
- 1409557
- Report Number(s):
- BNL-114609-2017-JA¿¿¿
- Journal Information:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 121, Issue 1; ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
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