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Title: Photoelectron Imaging and Spectroscopy of MI2- (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding

Abstract

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.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1012881
Report Number(s):
PNNL-SA-72233
25395; KC0301020; TRN: US201110%%398
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A, 114(42):11244-11251
Additional Journal Information:
Journal Volume: 114; Journal Issue: 42
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BONDING; COVALENCE; ELECTRON CORRELATION; ELECTRONS; GOLD; PHOTOELECTRON SPECTROSCOPY; SPECTRA; SPECTROSCOPY; Environmental Molecular Sciences Laboratory

Citation Formats

Wang, Yi-Lei, Wang, Xue B, Xing, Xiaopeng, Wei, Fan, Li, Jun, and Wang, Lai S. Photoelectron Imaging and Spectroscopy of MI2- (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding. United States: N. p., 2010. Web. doi:10.1021/jp103173d.
Wang, Yi-Lei, Wang, Xue B, Xing, Xiaopeng, Wei, Fan, Li, Jun, & Wang, Lai S. Photoelectron Imaging and Spectroscopy of MI2- (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding. United States. https://doi.org/10.1021/jp103173d
Wang, Yi-Lei, Wang, Xue B, Xing, Xiaopeng, Wei, Fan, Li, Jun, and Wang, Lai S. 2010. "Photoelectron Imaging and Spectroscopy of MI2- (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding". United States. https://doi.org/10.1021/jp103173d.
@article{osti_1012881,
title = {Photoelectron Imaging and Spectroscopy of MI2- (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding},
author = {Wang, Yi-Lei and Wang, Xue B and Xing, Xiaopeng and Wei, Fan and Li, Jun and Wang, Lai S},
abstractNote = {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.},
doi = {10.1021/jp103173d},
url = {https://www.osti.gov/biblio/1012881}, journal = {Journal of Physical Chemistry A, 114(42):11244-11251},
number = 42,
volume = 114,
place = {United States},
year = {Thu Oct 28 00:00:00 EDT 2010},
month = {Thu Oct 28 00:00:00 EDT 2010}
}