Grand Canonical Ensemble Modeling of Electrochemical Interfaces Made Simple

Xia, Zhaoming1,2; Xiao, Hai1

2023-07-01

10.1021/acs.jctc.3c00237

JOURNAL OF CHEMICAL THEORY AND COMPUTATION   影响因子和分区

1549-9618

1549-9626

Grand canonical ensemble (GCE) modelingof electrochemical interfaces,in which the electrochemical potential is converged to a preset constant,is essential for understanding electrochemistry and electrocatalysisat the electrodes. However, it requires developing efficient and robustalgorithms to perform practical and effective GCE modeling with densityfunctional theory (DFT) calculations. Herein, we developed an efficientand robust fully converged constant-potential (FCP) algorithm basedon Newton's method and a polynomial fitting to calculate thenecessary derivative for DFT calculations. We demonstrated with theconstant-potential geometry optimization and Born-Oppenheimermolecular dynamics (BOMD) calculations that our FCP algorithm is resistantto the numerical instability that plagues other algorithms, and itdelivers efficient convergence to the preset electrochemical potentialand renders accurate forces for updating the nuclear positions ofan electronically open system, outperforming other algorithms. Theimplementation of our FCP algorithm enables flexibility in using variouscomputational codes and versatility in performing advanced tasks includingthe constant-potential enhanced-sampling BOMD simulations that weshowcased with the modeling of the electrochemical hydrogenation ofCO, and it is thus expected to find a wide spectrum of applicationsin the modeling of chemistry at electrochemical interfaces.

SCI

英语

其他

National Natural Science Foundation of China["22122304","92261111"] ; Tsinghua University Dushi Program, National Key Research and Development Project[2022YFA1503000] ; Tsinghua University Initiative Scientific Research Program[20221080065] ; China Postdoctoral Science Foundation[2020M680507]

Chemistry ; Physics

Chemistry, Physical ; Physics, Atomic, Molecular & Chemical

WOS:001021435600001

AMER CHEMICAL SOC

Web of Science

1.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Xia, Zhaoming,Xiao, Hai. Grand Canonical Ensemble Modeling of Electrochemical Interfaces Made Simple[J]. JOURNAL OF CHEMICAL THEORY AND COMPUTATION,2023,19(15).

Xia, Zhaoming,&Xiao, Hai.(2023).Grand Canonical Ensemble Modeling of Electrochemical Interfaces Made Simple.JOURNAL OF CHEMICAL THEORY AND COMPUTATION,19(15).

Xia, Zhaoming,et al."Grand Canonical Ensemble Modeling of Electrochemical Interfaces Made Simple".JOURNAL OF CHEMICAL THEORY AND COMPUTATION 19.15(2023).