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Title: Photoelectron Spectroscopy and Theoretical Study of M(IO3)2– (M = H, Li, Na, K): Structural Evolution, Optical Isomers and Hyperhalogen Behavior

H(IO3)2- and M(IO3)2- (M = Li, Na, K) anions were successfully produced via electrospray ionization of their corresponding bulk salt solutions, and were characterized by combining negative ion photoelectron spectroscopy and quantum chemical calculations. The photoelectron spectra reveal that all these M(IO3)2- species possess very high vertical detachment energies (VDEs), to be 6.25, 6.57, 6.60 and 6.51 eV for H(IO3)2-, Li(IO3)2-, Na(IO3)2- and K(IO3)2-, respectively, which are much higher than that of IO3- (4.77 eV). The theoretical calculations show that each of these anions has two energetically degenerated optical isomers. It is found that the structure of H(IO3)2- can be written as IO3-(HIO3), in which the H atom is tightly bound to one of the IO3- groups and forms an iodic acid (HIO3) molecule; while the structures of M(IO3)2- can be written as (IO3-)M+(IO3-), in which the alkali metal atoms interact with the two IO3- groups almost equally and bridge the two IO3- groups via two O atoms of each IO3- with the two MOOI planes nearly perpendicular to each other. In addition, the high VDEs of M(IO3)2- (M = Li, Na, K) can be explained by the hyperhalogen behavior of their neutral counterparts.
Authors:
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Publication Date:
OSTI Identifier:
1092641
Report Number(s):
PNNL-SA-96268
44678; KC0301020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics, 139(4):Article No. 044312
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory