This study has proposed a Hückel theory-based extrapolation scheme for estimating the highest occupied molecular orbital (HOMO)-the lowest unoccupied molecular orbital (LUMO) gap of polymers without resorting to periodic boundary condition calculations using plane wave functions with hybrid functionals. The extrapolation scheme similar to ONIOM combines pure density functional theory (DFT) using plane wave functions for polymers and hybrid DFT using Gaussian functions for oligomers. We numerically assessed the scheme for polythiophene and 380 polymers and confirmed its accuracy and efficiency for polymer screening. Therefore, this scheme can be a screening methodology to estimate HOMO-LUMO energy gaps.

这项研究提出了一种基于Hückel理论的外推方案，用于估算聚合物的最高占据分子轨道（HOMO）-最低未占据分子轨道（LUMO）间隙，而无需借助使用具有混合功能的平面波函数进行周期性边界条件计算。类似于ONIOM的外推方案将使用平面波函数的纯密度泛函理论（DFT）用于聚合物，将使用高斯函数的混合DFT应用于低聚物。我们对聚噻吩和380聚合物的方案进行了数字评估，并证实了其筛选聚合物的准确性和效率。因此，该方案可以是一种筛选方法，用于估计HOMO-LUMO能隙。