Practical Approach to Large-Scale Electronic Structure Calculations in Electrolyte Solutions via Continuum-Embedded Linear-Scaling Density Functional Theory
Practical Approach to Large-Scale Electronic Structure Calculations in Electrolyte Solutions via Continuum-Embedded Linear-Scaling Density Functional Theory
复制标题
通过连续介质嵌入式线性尺度密度泛函理论进行电解质溶液中大规模电子结构计算的实用方法
DOI：
10.1021/acs.jpcc.0c00762
复制
发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Dziedzic J
中科院分区：
文献类型：
--
作者：
Dziedzic J
我们提出了一个混合连续原子模型的实施，包括周围的电解质的影响，在大规模的密度泛函理论（DFT）的计算内theOrder-N电子总能量包（ONETEP）线性尺度DFT代码，它允许模拟大型复杂系统，如电化学接口。该模型将电解质离子表示为标量场，将溶剂表示为可极化的介电连续体，两者都围绕着量子溶质。整体能量的表达是一个大正则函数，将电子动能和交换相关能量，总静电能，熵，周围电解质的化学势，渗透压，和空化，分散和排斥的影响。DFT计算在电解质模型中完全自洽地进行，允许量子力学系统和周围的连续环境相互作用和相互干扰。一个定制的高度并行的多重网格泊松-玻尔兹曼求解器库，DL_MG，处理静电问题，解决广义泊松-玻尔兹曼方程。我们的模型支持开放边界条件，这允许在电解质中处理分子、整个生物分子或较大的纳米颗粒组装体。我们还实现了周期性边界条件的模型，允许处理扩展系统，例如与电解质接触的电极表面。该模型的一个关键特点是使用溶质的大小和溶剂壳意识的可达性功能，防止非物理的电解质电荷的量子溶质边界附近的积累。该模型有少量的参数，在这里，我们证明了他们的校准实验平均活度系数。我们还提出了一个示例性的模拟石墨阳极和LiPF 6电解质在碳酸乙烯酯溶剂之间的界面的1634原子模型。我们比较的情况下，锂原子插入在相对的边缘的石墨板和溶液中，展示了潜在的应用模型在模拟锂离子电池的基本过程。
We present the implementation of a hybrid continuum-atomistic model for including the effects of a surrounding electrolyte in large-scale density functional theory (DFT) calculations within theOrder-NElectronic Total Energy Package (ONETEP)linear-scaling DFT code, which allows the simulation of large complex systems such as electrochemical interfaces. The model represents the electrolyte ions as a scalar field and the solvent as a polarizable dielectric continuum, both surrounding the quantum solute. The overall energy expression is a grand canonical functional incorporating the electron kinetic and exchange–correlation energies, the total electrostatic energy, entropy, and chemical potentials of the surrounding electrolyte, osmotic pressure, and the effects of cavitation, dispersion, and repulsion. The DFT calculation is performed fully self-consistently in the electrolyte model, allowing the quantum-mechanical system and the surrounding continuum environment to interact and mutually polarize. A bespoke highly parallel multigrid Poisson–Boltzmann solver library,DL_MG, deals with the electrostatic problem, solving a generalized Poisson–Boltzmann equation. Our model supports open boundary conditions, which allows the treatment of molecules, entire biomolecules, or larger nanoparticle assemblies in the electrolyte. We have also implemented the model for periodic boundary conditions, allowing the treatment of extended systems such as electrode surfaces in contact with the electrolyte. A key feature of the model is the use of solute size and solvation-shell-aware accessibility functions that prevent the unphysical accumulation of electrolyte charge near the quantum solute boundary. The model has a small number of parameters—here we demonstrate their calibration against experimental mean activity coefficients. We also present an exemplar simulation of an 1634-atom model of the interface between a graphite anode and LiPF6electrolyte in an ethylene carbonate solvent. We compare the cases where Li atoms are intercalated at opposite edges of the graphite slab and in solution, demonstrating a potential application of the model in simulations of fundamental processes in Li-ion batteries.
登录
查看更多内容
DOI：
10.1063/1.2168456
发表时间：
2005-10
期刊：
The Journal of chemical physics
影响因子：
--
作者：
D. Scherlis;J. Fattebert;F. Gygi;M. Cococcioni;N. Marzari
通讯作者：
D. Scherlis;J. Fattebert;F. Gygi;M. Cococcioni;N. Marzari
影响因子：
5.5
作者：
Stefan Ringe;H. Oberhofer;C. Hille;S. Matera;K. Reuter
通讯作者：
Stefan Ringe;H. Oberhofer;C. Hille;S. Matera;K. Reuter
DL_MG：用于真空和溶液中电子结构计算的并行多重网格泊松和泊松-玻尔兹曼求解器。
影响因子：
5.5
作者：
J. C. Womack;L. Anton;J. Dziedzic;P. Hasnip;Matt Probert;Chris
通讯作者：
Chris
DOI：
10.1063/1.4728026
发表时间：
2012-06
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Ãlvaro Ruiz-Serrano;N. Hine;Chris-Kriton Skylaris
通讯作者：
Ãlvaro Ruiz-Serrano;N. Hine;Chris-Kriton Skylaris
用于线性缩放电子结构计算的预处理迭代最小化
影响因子：
4.4
作者：
A. Mostofi;P. Haynes;Chris;M. Payne
通讯作者：
M. Payne