Rong Chunying, Zhao Dongbo, He Xin, Liu Shubin
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University, Changsha, Hunan410081, China.
Institute of Biomedical Research, Yunnan University, Kunming650500, Yunnan, China.
J Phys Chem Lett. 2022 Dec 8;13(48):11191-11200. doi: 10.1021/acs.jpclett.2c03165. Epub 2022 Nov 29.
Density functional theory, which is well-recognized for its accuracy and efficiency, has become the workhorse for modeling the electronic structure of molecules and extended materials in recent decades. Nevertheless, establishing a density-based conceptual framework to appreciate bonding, stability, function, reactivity, and other physicochemical properties is still an unaccomplished task. In this Perspective, we at first provide an overview of the four pathways currently available in the literature to tackle the matter, including orbital-free density functional theory, conceptual density functional theory, direct use of density-associated quantities, and the information-theoretic approach. Then, we highlight several recent advances of employing these approaches to realize new understandings for chemical concepts such as covalent bonding, noncovalent interactions, cooperation, frustration, homochirality, chirality hierarchy, electrophilicity, nucleophilicity, regioselectivity, and stereoselectivity. Finally, we provide a few possibilities for the future development of this relatively uncharted territory. Opportunities are abundant, and they are all ours for the taking.
密度泛函理论因其准确性和效率而广受认可，在近几十年来已成为模拟分子和扩展材料电子结构的主力军。然而，建立一个基于密度的概念框架来理解键合、稳定性、功能、反应性和其他物理化学性质仍是一项未完成的任务。在这篇展望文章中，我们首先概述了目前文献中可用于解决该问题的四种途径，包括无轨道密度泛函理论、概念密度泛函理论、直接使用与密度相关的量以及信息论方法。然后，我们强调了最近利用这些方法对诸如共价键、非共价相互作用、协同作用、受挫作用、同手性、手性层级、亲电性、亲核性、区域选择性和立体选择性等化学概念实现新理解的一些进展。最后，我们为这个相对未知领域的未来发展提供了一些可能性。机会众多，都有待我们去把握。
