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Spin Uncoupling in Chemisorbed OCCO and CO2: Two High-Energy Intermediates in Catalytic CO2 Reduction
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0001-6496-6865
Stockholm University, Faculty of Science, Department of Physics. Universidade Federal de Minas Gerais, Brazil.
Stockholm University, Faculty of Science, Department of Physics.
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Number of Authors: 62018 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 122, no 23, p. 12251-12258Article in journal (Refereed) Published
Abstract [en]

The production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO, covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spin uncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an average gross interaction energy of -1.82 eV/bond. The energy cost for electronically exciting OCCO- to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO2, conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of -2.07 eV. The 5.0 eV excitation energy to the CO2- quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.

Place, publisher, year, edition, pages
2018. Vol. 122, no 23, p. 12251-12258
National Category
Physical Sciences Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-158263DOI: 10.1021/acs.jpcc.8b02165ISI: 000435611900015OAI: oai:DiVA.org:su-158263DiVA, id: diva2:1236793
Available from: 2018-08-06 Created: 2018-08-06 Last updated: 2018-08-06Bibliographically approved

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Hedström, SvanteCampos dos Santos, EgonLiu, ChangChan, KarenAbild-Pedersen, FrankPettersson, Lars G. M.
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