Henderson Thomas M, Janesko Benjamin G, Scuseria Gustavo E
Department of Chemistry, Rice University, 6100 Main Street, Houston, Texas 77005-1892, USA.
J Phys Chem A. 2008 Dec 11;112(49):12530-42. doi: 10.1021/jp806573k.
Kohn-Sham density functional theory has become a standard method for modeling energetic, spectroscopic, and chemical reactivity properties of large molecules and solids. Density functional theory provides a rigorous theoretical framework for modeling the many-body exchange-correlation effects that dominate the computational cost of traditional wave function approaches. The advent of hybrid exchange-correlation functionals which incorporate a fraction of nonlocal exact exchange has solidified the prominence of density functional theory within computational chemistry. Hybrids provide accurate treatments of properties such as thermochemistry and molecular geometry. But they also exhibit some rather spectacular failures, and often contain multiple empirical parameters. This article reviews our work on developing novel exchange-correlation functionals that build upon the successes of global hybrids. We focus on more flexible functional forms, including local and range-separated hybrid functionals, constructed to obey known exact constraints and (ideally) to incorporate a minimum of empirical parametrization. The article places our work within the context of some other new approximate density functionals and discusses prospects for future work.
科恩-沈密度泛函理论已成为一种用于模拟大分子和固体的能量、光谱及化学反应活性性质的标准方法。密度泛函理论为模拟多体交换关联效应提供了一个严格的理论框架，而这种效应在传统波函数方法的计算成本中占主导地位。包含一部分非局部精确交换的杂化交换关联泛函的出现，巩固了密度泛函理论在计算化学中的突出地位。杂化泛函能对热化学和分子几何结构等性质进行精确处理。但它们也表现出一些相当惊人的失败之处，并且通常包含多个经验参数。本文回顾了我们在开发新型交换关联泛函方面的工作，这些泛函建立在全局杂化泛函成功的基础之上。我们专注于更灵活的泛函形式，包括局部和范围分离的杂化泛函，其构建方式是为了遵循已知的精确约束条件，并且（理想情况下）尽量减少经验参数化。本文将我们的工作置于其他一些新的近似密度泛函的背景下，并讨论了未来工作的前景。
