Molecular Simulation of CO2- and CO3-Brine-Mineral Systems
Molecular Simulation of CO2- and CO3-Brine-Mineral Systems
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DOI：
10.2138/rmg.2013.77.6
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发表时间：
2013
影响因子：
--
通讯作者：
Laura M. Hamm;I. Bourg;A. Wallace;B. Rotenberg
中科院分区：
文献类型：
--
作者：
Laura M. Hamm;I. Bourg;A. Wallace;B. Rotenberg
原子模拟--分子动力学(MD)和蒙特卡罗(MC)模拟、从头算和密度泛函理论(DFT)计算--已被证明有助于深入了解水生地球化学基本过程的分子基础，如溶剂化、离子对形成、吸附、分子扩散和矿物相的能量学(Rotenberg等人)。2007年；Bickmore等人。2009年；Hamm等人。2010年；Keriset和Liu，2010年；霍夫曼等人。2012年；Stack等人。2012年；华莱士等人。2013年)。这些模拟的关键优势在于它们能够检查单个原子的行为(光谱和其他实验方法探测大量分子的平均行为)，并允许在实验室施加难以或不可能施加的限制。这些特征使得原子模拟成为阐明地化系统中集体现象产生于分子尺度性质的方式的有力工具。原子模拟探测的长度和时间范围(从埃到几十纳米，从飞秒到微秒，随着计算资源的可用性和复杂性的进步而不断扩大)使它们非常适合于补充几种光谱技术，包括X射线、中子和核磁共振方法。本章所述方法的一个众所周知的局限性，特别是在经典力学(MD和MC)模拟的情况下，是用于描述原子间作用力的模型的近似性质。在这些模拟中，最简单的是键的长度和角度是固定的；原子间的相互作用被建模为只取决于相互作用原子的身份和它们之间的距离的两体相互作用的总和；在模拟期间不允许化学键断裂或形成(Allen和Tildesley 1987；Frenkel和Smit 2001)。力量…的选择
Atomistic simulations—molecular dynamics (MD) and Monte Carlo (MC) simulations, ab initio and density functional theory (DFT) calculations—have proved useful in gaining insight into the molecular basis of fundamental processes in aquatic geochemistry, such as solvation, ion pair formation, adsorption, molecular diffusion, and the energetics of mineral phases (Rotenberg et al. 2007; Bickmore et al. 2009; Hamm et al. 2010; Kerisit and Liu 2010; Hofmann et al. 2012; Stack et al. 2012; Wallace et al. 2013). Key strengths of these simulations are their ability to examine the behavior of individual atoms (where spectroscopic and other experimental methods probe the average behavior of large numbers of molecules) and to allow constraints that would be difficult or impossible to impose in the laboratory. These features make atomistic simulations powerful tools for elucidating the manner in which collective phenomena arise from molecular scale properties in geochemical systems. The range of length and time scales probed by atomistic simulations (from angstroms to tens of nanometers and from femtoseconds to microseconds, continuously expanding with advances in the availability and sophistication of computational resources) makes them ideally suited to complement several spectroscopic techniques, including X-ray, neutron, and nuclear magnetic resonance approaches. A well known limitation of the methods described in the present chapter, particularly in the case of classical mechanical (MD and MC) simulations, is the approximate nature of the models that are used to describe interatomic forces. In the simplest of these simulations, bond lengths and angles are fixed; inter-atomic interactions are modeled as the sum of two-body interactions that depend only on the identity of the interacting atoms and the distance between them; and chemical bonds are not allowed to break or form during a simulation (Allen and Tildesley 1987; Frenkel and Smit 2001). The choice of force …