Approximate Density Functional Theory as a Practical Tool in Molecular Energetics and Dynamics
Approximate Density Functional Theory as a Practical Tool in Molecular Energetics and Dynamics
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DOI：
10.1002/chin.199203329
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发表时间：
1991-07
期刊：
影响因子：
--
通讯作者：
T. Ziegler
中科院分区：
文献类型：
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作者：
T. Ziegler
近似密度泛函理论（DFT）在过去的十年中已经成为一种有形的和通用的计算方法。它已被成功地用于获得热化学数据，分子结构，力场和频率，核磁共振，光电子，ESR和紫外光谱的分配，过渡态结构，以及激活势垒，偶极矩和其他单电子性质。因此，近似DFT现在被应用于许多以前只由从头算Hartree-Fock （HF）和post-HF方法覆盖的问题。近似DFT最近的流行在很大程度上源于它的计算便捷性，这使得它可以在HF或后HF计算所需的一小部分时间内适用于大尺寸或现实分子。也许更重要的是，在大多数情况下，由近似DFT得到的期望值比由高频计算得到的结果更符合实验。涉及过渡金属的系统尤其如此。本文的主要目的是通过对分子性质的计算来评估近似DFT的准确性。将进一步强调与高频法和微波法获得的精度进行比较
I. Introduction Approximate density functional theory (DFT) has over the pastdecade emerged as a tangible and versatile computational method. It has been employed suc-cessfully to obtain thermochemical data, molecular structures, force fields and frequencies, assignments of NMR, photoelectron, ESR, and UV spectra, transition-state structures, as well as activation barriers, di-pole moments, andother one-electron properties. Thus, approximate DFT is now applied to many problems previously covered exclusively by ab initio Hartree-Fock (HF) and post-HF methods. The recently ac-quired popularity of approximate DFT stems in large measure from its computational expedience which makes it amenable to large-size or real-life molecules at a fraction of the time required for HF or post-HF calculations. More importantly, perhaps, is the factthat expectation values derived from approximate DFT in most cases are better in line with experiment than re-sults obtained from HF calculations. This is in par-ticular the case for systems involving transition metals. It is the primary objective of this review to assess the accuracy of approximate DFT by evaluating DFT re-sults from calculations on a number of molecular properties. Emphasis will further be given to a com-parison with the degree of accuracy obtained by HF and