Lee Jung-Hoon, Lee Sang-Hoon, Son Young-Woo
Computational Science Research Center, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea.
KU-KIST Graduate School of Converging Science and Technology, Korea University, Seoul 02841, Republic of Korea.
J Chem Theory Comput. 2025 Jul 22;21(14):6922-6932. doi: 10.1021/acs.jctc.5c00818. Epub 2025 Jun 29.
We present a comprehensive benchmarking study of first-principles calculation methods, based on density functional theory (DFT) and its extensions, to evaluate the fundamental and optical band gaps of nanoporous materials, including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), and a zeolite. We find that a hybrid approach using the HSE06 functional generally underestimates the fundamental band gaps compared to the nonself-consistent GW (GW) approximation, and a DFT approach incorporating self-consistent extended Hubbard interactions shows varying agreement with GW results depending on the electronic characteristics of materials. Using the Bethe-Salpeter equation (BSE) on top of GW calculations (GW+BSE) and time-dependent DFT (TDDFT) with the PBE functional, we compute optical band gaps and absorption spectra that are in good agreement with experiments. In particular, GW+BSE outperforms TDDFT with mean absolute errors (MAEs) of 0.68 and 1.00 eV, respectively, for the computed optical band gaps. Furthermore, we find that exciton binding energies in nanoporous materials are significantly larger than those of inorganic systems, attributed to the spatial localization of the valence band maximum (VBM) and conduction band minimum (CBM) on the same structural subunit. These results provide valuable insights into the performance of different computational methodologies for nanoporous materials and offer practical guidance for the development and application of first-principles approaches in materials with high porosity.
我们基于密度泛函理论（DFT）及其扩展，对第一性原理计算方法进行了全面的基准测试研究，以评估包括金属有机框架（MOF）、共价有机框架（COF）和沸石在内的纳米多孔材料的基本带隙和光学带隙。我们发现，与非自洽GW（GW）近似相比，使用HSE06泛函的混合方法通常会低估基本带隙，并且结合自洽扩展哈伯德相互作用的DFT方法与GW结果的一致性因材料的电子特性而异。在GW计算（GW + BSE）之上使用贝叶斯 - 萨尔皮特方程（BSE）以及使用PBE泛函的含时DFT（TDDFT），我们计算出与实验结果高度吻合的光学带隙和吸收光谱。特别是，对于计算出的光学带隙，GW + BSE的表现优于TDDFT，平均绝对误差（MAE）分别为0.68和1.00 eV。此外，我们发现纳米多孔材料中的激子结合能明显大于无机体系中的激子结合能，这归因于价带最大值（VBM）和导带最小值（CBM）在同一结构亚基上空间定位。这些结果为纳米多孔材料不同计算方法的性能提供了有价值的见解，并为高孔隙率材料中第一性原理方法的开发和应用提供了实际指导。
