Spin Uncoupling in Chemisorbed OCCO and CO<sub>2</sub> [electronic resource] : Two High-Energy Intermediates in Catalytic CO<sub>2</sub> Reduction
- Washington, D.C. : United States. Dept. of Energy, 2018. and Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
- Physical Description:
- pages 12,251-12,258 : digital, PDF file
- Additional Creators:
- SLAC National Accelerator Laboratory, United States. Department of Energy, and United States. Department of Energy. Office of Scientific and Technical Information
- Here, 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<sub>2</sub> 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. CO<sub>2</sub>, 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 CO<sub>2</sub><sup>–</sup> quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.
- Published through SciTech Connect., 05/08/2018., Journal of Physical Chemistry. C 122 23 ISSN 1932-7447 AM, and Svante Hedstrom; Egon Campos dos Santos; Chang Liu; Karen Chan; Frank Abild-Pedersen; Lars G. M. Pettersson.
- Funding Information:
- 348-2013-6723, 42024-1, KAW-2013.0020, KAW- 2016.0042, and AC02-76SF00515
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