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Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer

Chen, Leanne D. and Bajdich, Michal and Martirez, J. Mark P. and Krauter, Caroline and Gauthier, Joseph A. and Carter, Emily Ann and Luntz, Alan C. and Chan, Karen and Nørskov, Jens K. (2019) Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer. In: 257th ACS National Meeting & Exposition, 31 March - 4 April 2019, Orlando, FL.

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A detailed at.-scale description of the electrochem. interface is essential to the understanding of electrochem. Energy transformations. In this work, we investigate the charge of solvated protons at the Pt(111) | H_2O and Al(111) | H_2O interfaces. Using semi-local d.-functional theory as well as hybrid functionals and embedded correlated wavefunction methods as higher-level benchmarks, we show that the effective charge of a solvated proton in the electrochem. double layer or outer Helmholtz plane at all levels of theory is fractional, when the solvated proton and solvent band edges are aligned correctly with the Fermi level of the metal (E_F). The obsd. fractional charge in the absence of frontier band misalignment arises from a significant overlap between the proton and the electron d. from the metal surface, and results in an energetic difference between protons in bulk soln. and those in the outer Helmholtz plane.

Item Type:Conference or Workshop Item (Paper)
Related URLs:
URLURL TypeDescription Website ItemJournal Article
Chen, Leanne D.0000-0001-9700-972X
Bajdich, Michal0000-0003-1168-8616
Martirez, J. Mark P.0000-0003-0566-6605
Carter, Emily Ann0000-0001-7330-7554
Chan, Karen0000-0002-6897-1108
Additional Information:© 2019 American Chemical Society.
Record Number:CaltechAUTHORS:20190312-104711444
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:93734
Deposited By: Tony Diaz
Deposited On:12 Mar 2019 18:07
Last Modified:03 Oct 2019 20:57

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