Essentials Of Computational Chemistry Theories And Models
Essentials Of Computational Chemistry Theories And Models
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发表时间：
2016
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通讯作者：
M. Keller
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作者：
M. Keller
一本介绍计算化学基础知识的新教科书包含 500 多页，这一事实令人印象深刻地表明了这一化学领域不断增长的规模和重要性。用作者自己的话来说，这本书的目标是“提供对计算化学的基础、术语、优点和缺点的调查，以便实验和理论界都能理解”。这种设计作为计算化学的一般介绍，使其成为安德鲁·R·利奇（Andrew R. Leach）完善的“分子建模”（Prentice Hall）和弗兰克·詹森（Frank Jensen）的“计算化学导论”（Wiley）的替代品，尽管后者侧重于电子结构方法的理论。克莱默的“要点”涵盖了力场和分子轨道理论、蒙特卡罗和分子动力学模拟、热力学和电子（光谱）性质计算、凝聚相处理以及其他一些主题。此外，本书还包含从文献中选取的十三个案例研究示例，以说明刚刚提出的理论和计算模型的应用。这尤其使得本书非常适合课堂讨论和自学。 《精要》的每一章都涵盖了计算化学的一个主要主题，这里将进行简要介绍；所有章节均以参考书目、建议的附加读物以及文中引用的文献参考结尾。在第一章中，作者定义了“理论”、“模型”和“计算”等基本术语，介绍了势能面的概念，并提供了一些有关硬件和软件的一般考虑。有趣的是，文本中出现的第一个方程并不是大多数计算化学介绍中的薛定谔方程，而是著名的爱因斯坦关系式。第二章涉及分子力学。它解释了不同的势能贡献，介绍了结构优化领域，并概述了各种现代力场。第 3 章介绍了分子系综的模拟。它定义了相空间和轨迹，并展示了蒙特卡罗和分子动力学的形式主义、问题和区别。在第四章中，作者介绍了分子轨道理论的基础。解释了Hamilton算子、LCAO基组方法、多电子波函数等基本概念。为了阐明 LCAO 变分过程，以 Hückel 理论为例。第五章讨论半经验分子轨道（MO）理论。除了经典方法（扩展 Hu ̈ckel、CNDO、INDO、NDDO）和方法（例如 MNDO、AM1、PM3）及其性能之外，还提供了该仍然令人着迷的领域中正在进行的开发的示例。第六章介绍了从头开始的 MO 理论；详细讨论了基组概念，并从用户的角度进行了一些考虑后，阐明了从头开始方法的一般性能。下一章讨论电子关联问题，并给出其处理的最突出的解决方案：构型相互作用、多构型自洽场理论、扰动和耦合簇。还讨论了实际问题。第 8 章的主题是密度泛函理论（DFT）。介绍了它的理论基础、方法论和一些泛函，以及与 MO 理论相比的优缺点，并进行了总体性能概述。接下来的两章讨论电荷分布、导出和光谱特性（例如，原子电荷、极化率、旋转、振动和核磁共振谱）和热力学特性（例如，零点振动能、形成自由能和反应）。第 11 章（隐式模型）和第 12 章（显式模型）讨论了凝聚相的建模，最后对两种方法进行了比较。第 13 章让读者熟悉混合量子力学/分子力学 (QM/MM) 模型。讨论了极化以及不饱和 QM 和 MM 成分的问题含义，并提出了经验价键方法。激发态的处理是第 14 章的主题；除了 CI 和 MCSCF 作为计算方法外，还讨论了跃迁概率和溶剂化显色现象。最后一章讨论反应动力学，主要是绝热动力学，速率常数，反应路径和过渡态理论是本节的主题，但也是非绝热的，简要介绍了曲线交叉和马库斯理论。附录分为四个部分：首字母缩略词术语表（非常有帮助）、对称性和群论概述、自旋代数介绍，最后是关于轨道定位的部分。本书最后有一个相当详细的索引。 “精华”的写作风格适合这个引人入胜的主题：读下去就会惊喜！另一章已被吸收。文本辅以大量黑白图形和清晰的表格，大部分是不言自明的，并带有描述性标题。方程和数学公式的使用总体上是均衡的，并且数学水平对于每个具有一定物理基础知识的自然科学家来说应该是可以理解的。只有一些小缺点：例如，参考书目中缺少文本中引用的文献参考文献（“Beck et al.”，第 142 页）； “Kronecker” 拼写错误为 o ̈；作者在参考其他计算化学介绍时完全忘记参考利奇的教科书。然而，作者建立了一个特定的勘误网页（http://pollux.chem.umn.edu/∼cramer/Errors.html），其中包含所有已知错误。这些将分别在下一次印刷或下一次修订版本中进行更正。 《精要》一方面强调基本概念和应用，而不是纯粹的理论和数学，另一方面涵盖量子力学和经典力学模型，包括无机化学、有机化学和生物化学的例子，不仅是教学的有用工具，而且可以作为快速参考，因此很可能成为计算化学的标准教科书之一。
The fact that a new text book introducing the essentials of computational chemistry contains more than 500 pages shows impressively the grown and still growing size and importance of this field of chemistry. The author’s objectives of the book, using his own words, are “to provide a survey of computational chemistry its underpinnings, its jargon, its strengths and weaknesses that will be accessible to both the experimental and theoretical communities”. This design as a general introduction into computational chemistry makes it an alternative to Andrew R. Leach’s well-established “Molecular Modeling” (Prentice Hall) and Frank Jensen’s “Introduction to Computational Chemistry” (Wiley), although the latter focuses on the theory of electronic structure methods. Cramer’s “Essentials” covers force field and molecular orbital theory, Monte Carlo and Molecular Dynamics simulations, thermodynamic and electronic (spectroscopic) property calculation, condensed phase treatment and a few more topics. Moreover, the book contains thirteen selected case studies sexamples taken from the literature sto illustrate the application of the just presented theoretical and computational models. This especially makes the text book well suited for both classroom discussion and self-study. Each chapter of “Essentials” covers a main topic of computational chemistry and will be briefly described here; all chapters are ended by a bibliography and suggested additional readings as well as the literature references cited in the text. In chapter 1 the author defines basic terms such as “theory”, “model”, and “computation”, introduces the concept of the potential energy surface and provides some general considerations about hardware and software. Interestingly, the first equation occurring in the text is not Schro ̈dinger’s equation, as is the case for most computational chemistry introductions, but the famous Einstein relation. The second chapter deals with molecular mechanics. It explains the different potential energy contributions, introduces the field of structure optimization, and provides an overview of the variety of modern force fields. Chapter 3 covers the simulation of molecular ensembles. It defines phase space and trajectories and shows the formalism of, and problems and difference between, Monte Carlo and molecular dynamics. In chapter 4 the author introduces the foundations of molecular orbital theory. Basic concepts such as Hamilton operator, LCAO basis set approach, many-electron wave functions, etc. are explained. To illuminate the LCAO variational process, the Hu ̈ckel theory is presented with an example. Chapter 5 deals with semiempirical molecular orbital (MO) theory. Besides the classical approaches (extended Hu ̈ckel, CNDO, INDO, NDDO) and methods (e.g., MNDO, AM1, PM3) and their performance, examples are provided from the ongoing development in that still fascinating area. Ab initio MO theory is presented in chapter 6; the basis set concept is discussed in detail, and, after some considerations from an user’s point of view, the general performance of ab initio methods is explicated. The next chapter covers the problem of electron correlation and gives the most prominent solutions for its treatment: configuration interaction, theory of the multiconfiguration self-consistent field, perturbation, and coupled cluster. Practical issues are also discussed. Chapter 8’s topic is density functional theory (DFT). Its theoretical foundation, methodology, and some functionals as well as its pros and cons compared to MO theory are presented together with a general performance overview. The next two chapters deal with charge distribution, derived and spectroscopic properties (e.g., atomic charges, polarizability, rotational, vibrational, and NMR spectra), and thermodynamic properties (e.g., zero-point vibrational energy, free energy of formation, and reaction). The modeling of condensed phases is addressed in chapters 11 (implicit models) and 12 (explicit models), which closes with a comparison between the two approaches. Chapter 13 familiarizes the reader with hybrid quantum mechanical/molecular mechanical (QM/MM) models. Polarization as well as the problematic implications of unsaturated QM and MM components are discussed, and empirical valence bond methods are also presented. The treatment of excited states is the topic of chapter 14; besides CI and MCSCF as computational methods, transition probabilities and solvatochromism are discussed. The last chapter deals with reaction dynamics, mostly adiabaticskinetics, rate constants, reaction paths, and transition state theory are section topics here sbut also nonadiabatic, introducing curve crossing and Marcus theory in brief. The appendix is divided into four parts: an acronym glossary (which is very helpful), an overview of symmetry and group theory, an introduction to spin algebra, and finally a section about orbital localization. A rather detailed index ends the book. The “Essentials” writing style fits the fascinating topic: one reads on and on andssurprise! sanother chapter has been absorbed. The text is complemented by a large number of black and white figures and clear tables, mostly self-explanatory with descriptive captions. The use of equations and mathematical formulas in general is well-balanced, and the level of math should be understandable for every natural scientist with some basic knowledge of physics. There are only a few minor shortcomings: for example, a literature reference cited in the text (“Beck et al.”, p 142) is missing in the bibliography; “Kronecker” is mistyped with o ̈; and the author completely forgot to reference Leach’s text book when referring to other computational chemistry introductions. However, the author has established a specific errata web page (http://pollux.chem.umn.edu/ ∼cramer/Errors.html) with all known errors. These will be corrected in the next printing or next revised edition, respectively. With its emphasis, on one hand, on the basic concepts and applications rather than pure theory and mathematics, and on the other hand, coverage of quantum mechanical and classical mechanical models including examples from inorganic, organic, and biological chemistry, “Essentials” is a useful tool not only for teaching and learning but also as a quick reference, and thus will most probably become one of the standard text books for computational chemistry.