标题： 石墨烯共价功能化的DFT建模：从理想到现实模型 显示英文标题

标题： DFT modeling of the covalent functionalization of graphene: from ideal to realistic models

摘要： 多类石墨烯的制备，例如独立式石墨烯、碳化硅和金属上的外延石墨烯、溶液中的石墨烯、化学生长的类石墨烯分子、各类石墨烯纳米带以及不同还原程度和化学成分不同的氧化石墨烯，表明需要进一步研究超越石墨烯功能化基本原理的内容，以避免从第一性原理模拟预测与实验结果之间偶尔出现的矛盾。 在此，我们讨论了使用密度泛函理论（DFT）方法对不同类型石墨烯建模的现状。 我们重点关注静态（基底、形状、曲率、应变和掺杂）和动态（功能化起始点、迁移势垒及构型稳定性）方面，这些方面提供了更正确且更具选择性的对各种化学物质在石墨烯支架上化学吸附的建模。 基于最近对实验实现的不同类型石墨烯功能化的建模，我们可以得出结论，早期研究中讨论的均匀单面或双面功能化石墨烯的形成是石墨烯化学中典型情况的例外。 不同基底、缺陷和晶格畸变（如褶皱和应变）的存在导致功能团形成簇或线。 在理想模型中发现了几种石墨烯基底上化学物质的构型，但它们仅在特定条件下功能化的石墨烯中稳定。 还讨论了技术参数（如使用的泛函和计算方法）的作用，以及对不同类型石墨烯化学性质建模的重要指导原则。 显示英文摘要

摘要： The production of multiple types of graphene, such as free standing, epitaxial graphene on silicon carbide and metals, graphene in solution, chemically grown graphene-like molecules, various graphene nanoribbons, and graphene oxide with different levels of reduction and various chemical composition, demonstrate the need for additional investigation beyond the basic principles of graphene functionalization for avoidance of occasionally contradictions between the predictions from first-principles simulations and experimental results. Herein, we discuss the current state of modeling of the different types of graphene using density functional theory (DFT) methods. We focus on the static (substrate, shape, curvature, strain and doping) and dynamic (starting point of functionalization, migration barriers and stability of configurations) aspects that provide a more correct and selective modeling of the chemisorption of various chemical species on the graphene scaffold. Based on the recent modeling of experimentally realized functionalization of different types of graphene we can conclude that the formation of uniform one- or two-sided functionalized graphene discussed in earlier studies is an exception to the typical scenarios of graphene chemistry. The presence of different substrates, defects and lattice distortions, such as ripples and strain, results in the formation of clusters or lines from the functional groups. Several configurations of the chemical species on the graphene substrate have been found to exist with ideal models but are only stable for graphene functionalized under special conditions. The role of the technical parameters, such as the functionals and computational methods employed, and the important guidelines for the modeling of the chemical properties of various types of graphene are also discussed.