Spectroscopic evidence for intact carbonic acid stabilized by halide anions in the gas phase
Physical Chemistry Chemical Physics, ISSN: 1463-9076, Vol: 22, Issue: 35, Page: 19459-19467
2020
- 10Citations
- 5Captures
- 10Mentions
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Article Description
This work shows elusive carbonic acid being effectively stabilized in the gas phase by interacting with halide anions X(X = F, Cl, Br, and I). The formed HCO·Xcomplexes, characterized by negative ion photoelectron spectroscopy andab initiocalculations, all contain intacttrans-transcarbonic acid binding onto the respective halideviatwo identical strong ionic O-H⋯Xhydrogen bonds. For X = Cl, Br, and I, the complex spectra exhibit the corresponding Xsignature by simply shifting to the higher binding energy side, while an extremely 2 eV wide broader band is observed for X = F. This spectroscopic evidence indicates that an excess electron is removed from each halide in the former case, while a proton is transferred from carbonic acid to fluoride upon electron detachment for the latter. The above HCO·Xstructures as well as those of the previously studied HSO·Xalong the homologous halogen series cannot be explained using the proton affinity (PA) argument. Instead, a qualitative correlation is found between these structural motifs and the constituent acid pKvalues, strongly suggesting that pKis a more suitable factor to predict correct acid-base chemistry between these diprotic oxyacids and halides.
Bibliographic Details
http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=85090051731&origin=inward; http://dx.doi.org/10.1039/d0cp02338h; http://www.ncbi.nlm.nih.gov/pubmed/32578641; https://xlink.rsc.org/?DOI=D0CP02338H; https://dx.doi.org/10.1039/d0cp02338h; https://pubs.rsc.org/en/content/articlelanding/2020/cp/d0cp02338h
Royal Society of Chemistry (RSC)
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