In molecular modeling of electrical double layers(EDLs),the constant charge method(CCM)is prized for its computational efficiency but cannot maintain electrode equipotentiality like the more resourceintensive constant...In molecular modeling of electrical double layers(EDLs),the constant charge method(CCM)is prized for its computational efficiency but cannot maintain electrode equipotentiality like the more resourceintensive constant potential method(CPM),potentially leading to inaccuracies.In certain scenarios,CCM can yield results identical to CPM.However,there are no clear guidelines to determine when CCM is sufficient and when CPM is required.Here,we conduct a series of molecular simulations across various electrodes and electrolytes to present a comprehensive comparison between CCM and CPM under different charging modes.Results reveal that CCM approximates CPM effectively in capturing equilibrium EDL and current-driven dynamics in open electrode systems featuring ionic liquids or regular concentration aqueous electrolytes,while CPM is indispensable in scenarios involving organic and highly concentrated aqueous electrolytes,nanoconfinement effects,and voltage-driven dynamics.This work helps to select appropriate methods for modeling EDL systems,prioritizing accuracy while considering computationalefficiency.展开更多
Aluminum anodization process requires a lot of electrical energy for the migration of ions in a barriertype oxide film,in which electrode polarization leads to massive energy consumption.The cathodes are considered to...Aluminum anodization process requires a lot of electrical energy for the migration of ions in a barriertype oxide film,in which electrode polarization leads to massive energy consumption.The cathodes are considered to be modified with catalysts,reducing their hydrogen evolution reaction(HER)overpotential in order to improve its energy utilization efficiency.展开更多
基金the funding support from the National Natural Science Foundation of China(T2325012 and 52161135104)the Program for HUST Academic Frontier Youth Team.
文摘In molecular modeling of electrical double layers(EDLs),the constant charge method(CCM)is prized for its computational efficiency but cannot maintain electrode equipotentiality like the more resourceintensive constant potential method(CPM),potentially leading to inaccuracies.In certain scenarios,CCM can yield results identical to CPM.However,there are no clear guidelines to determine when CCM is sufficient and when CPM is required.Here,we conduct a series of molecular simulations across various electrodes and electrolytes to present a comprehensive comparison between CCM and CPM under different charging modes.Results reveal that CCM approximates CPM effectively in capturing equilibrium EDL and current-driven dynamics in open electrode systems featuring ionic liquids or regular concentration aqueous electrolytes,while CPM is indispensable in scenarios involving organic and highly concentrated aqueous electrolytes,nanoconfinement effects,and voltage-driven dynamics.This work helps to select appropriate methods for modeling EDL systems,prioritizing accuracy while considering computationalefficiency.
基金supported by the National Natural Science Foundation of China(Granted No.51777152)the Natural Science Foundation of Shaanxi Province(Granted No.2019JLZ-09,2021JZ-01)the Fundamental Research Funds for the Central Universities(Granted No.XJJ2018055).
文摘Aluminum anodization process requires a lot of electrical energy for the migration of ions in a barriertype oxide film,in which electrode polarization leads to massive energy consumption.The cathodes are considered to be modified with catalysts,reducing their hydrogen evolution reaction(HER)overpotential in order to improve its energy utilization efficiency.
