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Title: Electrophilicity of oxalic acid monomer is enhanced in the dimer by intermolecular proton transfer

Abstract

We have analyzed the effect of excess electron attachment on the network of hydrogen bonds in the oxalic acid dimer (OA) 2. The most stable anionic structures may be viewed as complexes of a neutral hydrogenated moiety HOA˙ coordinated to an anionic deprotonated moiety (OA–H) -. HOA˙ acts as a double proton donor and (OA–H) - as a double proton acceptor. Thus the excess electron attachment drives intermolecular proton transfer. We have identified several cyclic hydrogen bonded structures of (OA) 2 -. Their stability has been analyzed in terms of the stability of the involved conformers, the energetic penalty for deformation of these conformers to the geometry of the dimer, and the two-body interaction energy between the deformed HOA˙ and (OA–H) -. There are at least seven isomers of (OA) 2 - with stabilization energies in the range of 1.26–1.39 eV. These energies are dominated by attractive two-body interaction energies. The anions are vertically bound electronically by 3.0–3.4 eV and adiabatically bound by at least 1.6 eV. The computational predictions are consistent with the anion photoelectron spectrum of (OA) 2 -. The spectrum consists of a broad feature, with an onset of 2.5 eV and spanning to 4.3 eV. Themore » electron vertical detachment energy (VDE) is assigned to be 3.3 eV.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [2];  [2]
  1. Institute of Chemical Sciences; School of Engineering and Physical Sciences; Heriot-Watt University; Edinburgh; UK
  2. Department of Chemistry; Johns Hopkins University; Baltimore; USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1492370
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 19; Journal Issue: 44; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Keolopile, Zibo G., Ryder, Matthew R., Calzada, Benjamin, Gutowski, Maciej, Buytendyk, Allyson M., Graham, Jacob D., and Bowen, Kit H. Electrophilicity of oxalic acid monomer is enhanced in the dimer by intermolecular proton transfer. United States: N. p., 2017. Web. doi:10.1039/c7cp00474e.
Keolopile, Zibo G., Ryder, Matthew R., Calzada, Benjamin, Gutowski, Maciej, Buytendyk, Allyson M., Graham, Jacob D., & Bowen, Kit H. Electrophilicity of oxalic acid monomer is enhanced in the dimer by intermolecular proton transfer. United States. doi:10.1039/c7cp00474e.
Keolopile, Zibo G., Ryder, Matthew R., Calzada, Benjamin, Gutowski, Maciej, Buytendyk, Allyson M., Graham, Jacob D., and Bowen, Kit H. Sun . "Electrophilicity of oxalic acid monomer is enhanced in the dimer by intermolecular proton transfer". United States. doi:10.1039/c7cp00474e.
@article{osti_1492370,
title = {Electrophilicity of oxalic acid monomer is enhanced in the dimer by intermolecular proton transfer},
author = {Keolopile, Zibo G. and Ryder, Matthew R. and Calzada, Benjamin and Gutowski, Maciej and Buytendyk, Allyson M. and Graham, Jacob D. and Bowen, Kit H.},
abstractNote = {We have analyzed the effect of excess electron attachment on the network of hydrogen bonds in the oxalic acid dimer (OA)2. The most stable anionic structures may be viewed as complexes of a neutral hydrogenated moiety HOA˙ coordinated to an anionic deprotonated moiety (OA–H)-. HOA˙ acts as a double proton donor and (OA–H)- as a double proton acceptor. Thus the excess electron attachment drives intermolecular proton transfer. We have identified several cyclic hydrogen bonded structures of (OA)2-. Their stability has been analyzed in terms of the stability of the involved conformers, the energetic penalty for deformation of these conformers to the geometry of the dimer, and the two-body interaction energy between the deformed HOA˙ and (OA–H)-. There are at least seven isomers of (OA)2- with stabilization energies in the range of 1.26–1.39 eV. These energies are dominated by attractive two-body interaction energies. The anions are vertically bound electronically by 3.0–3.4 eV and adiabatically bound by at least 1.6 eV. The computational predictions are consistent with the anion photoelectron spectrum of (OA)2-. The spectrum consists of a broad feature, with an onset of 2.5 eV and spanning to 4.3 eV. The electron vertical detachment energy (VDE) is assigned to be 3.3 eV.},
doi = {10.1039/c7cp00474e},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 44,
volume = 19,
place = {United States},
year = {2017},
month = {1}
}

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