Photoelectron Imaging and Spectroscopy of MI2- (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding
We report a combined experimental and theoretical investigation on MI2- (M = Cs, Cu, Ag, Au) to explore the chemical bonding in the group IA and IB di-iodide complexes. Both photoelectron imaging and low-temperature photoelectron spectroscopy are applied to MI2- (M = Cs, Cu, Au), yielding vibrationally resolved spectra for CuI2- and AuI2- and accurate electron affinities, 4.52 ± 0.02, 4.256 ± 0.010, and 4.226 ± 0.010 eV for CsI2, CuI2, and AuI2, respectively. Spin-orbit coupling is found to be important in all the di-iodide complexes and ab initio calculations including spin-orbit effects allow quantitative assignments of the observed photoelectron spectra. A variety of chemical bonding analyses (charge population, bond order, and electron localization functions) have been carried out, revealing a gradual transition from the expected ionic behavior in CsI2- to strong covalent bonding in AuI2-. Both relativistic effects and electron correlation are shown to enhance the covalency in the gold di-iodide complex.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1012881
- Report Number(s):
- PNNL-SA-72233; 25395; KC0301020; TRN: US201110%%398
- Journal Information:
- Journal of Physical Chemistry A, 114(42):11244-11251, Vol. 114, Issue 42
- Country of Publication:
- United States
- Language:
- English
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