TY - JOUR
T1 - Voltage-dependent cluster expansion for electrified solid-liquid interfaces
T2 - Application to the electrochemical deposition of transition metals
AU - Weitzner, Stephen E.
AU - Dabo, Ismaila
N1 - Funding Information:
The authors acknowledge primary support from the National Science Foundation under Grant No. DMR-1654625, and partial support from the Center for Dielectrics and Piezoelectrics at Penn State University. This research or portions of this research were conducted with Advanced CyberInfrastructure computational resources provided by The Institute for CyberScience at The Pennsylvania State University ( http://ics.psu.edu ). This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant No. ACI-1548562.
Publisher Copyright:
© 2017 American Physical Society.
PY - 2017/11/17
Y1 - 2017/11/17
N2 - The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.
AB - The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.
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U2 - 10.1103/PhysRevB.96.205134
DO - 10.1103/PhysRevB.96.205134
M3 - Article
AN - SCOPUS:85039944957
VL - 96
JO - Physical Review B-Condensed Matter
JF - Physical Review B-Condensed Matter
SN - 2469-9950
IS - 20
M1 - 205134
ER -