酞菁及其过渡金属配合物与富勒烯非共价相互作用的密度泛函理论方法研究

Screening of density functional theory methods for the study of non-covalent interactions between phthalocyanines and their transition metal complexes and fullerenes

精确计算酞菁、卟啉及其过渡金属配合物与富勒烯分子间非共价相互作用能,探讨其相互作用本质,需要完成由上百个原子构成的超分子复合物、涉及数千个基函数第一性原理计算,对于当前的理论方法和计算机发展水平都构成严峻的挑战.本文首先选择酞菁…C_(60)、酞菁镍…C_(60)和酞菁锌…C_(60)作为此类非共价复合物的代表.在保留它们分子间相互作用区域结构特征前提下,裁剪成四氮杂卟啉…碗烯、四氮杂卟啉镍…碗烯和四氮杂卟啉锌…碗烯三个模型.通过大规模的CCSD(T)/CBS计算,获得了此三个模型的达到化学精度的分子间相互作用能.以此为基准,从27种密度泛函及其色散和非局域校正方法中,筛选出ωB97M-V,ωB97X-D和BLYP-D3BJ方法,其结果与CCSD(T)/CBS基准值相差均在化学精度范围,特别是ωB97M-V方法,最大误差仅为0.05 kcal/mol,很好地重现了CCSD(T)/CBS的计算结果,说明ωB97M-V方法不仅适用于主族元素分子间非共价相互作用的研究,对于涉及Ni,Zn等闭壳层过渡金属配合物与富勒烯相互作用能计算同样是非常优秀的方法.

Accurately calculating the non-covalent interaction energies of phthalocyanines,porphyrins and their transition metal complexes with fullerenes,and exploring the nature of the interactions involve supramolecular complexes composed of hundreds of atoms and thousands of basis functions.The need to use first-principles methods to perform large-scale calculations is a challenge to current theoretical methods,computer hardware and software.In this paper,The phthalocyanine…C_(60),Ni-phthalocyanine…C_(60),and Zn-phthalocyanine…C_(60) are selected as representatives of such non-covalent complexes.Retaining the structural characteristics of their intermolecular interaction regions,and tailored into 3 models of porphyrazine…Corannulene,Ni-porphyrazine…Corannulene,and Zn-porphyrazine…Corannulene.For these 3 models,large-scale CCSD(T)/CBS calculations were carried out,and the intermolecular interaction energies with chemical precision were obtained.Using this as a standard,we have screened out theωB97M-V,ωB97X-D and BLYP-D3BJ methods from 27 common DFT methods for non-covalent interaction studies,and the difference between the intermolecular interaction energy results and the CCSD(T)/CBS results is less than 1 kcal/mol.In particular,for theωB97M-V method,the maximum error is only 0.05 kcal/mol,which almost reproduces the calculation results of CCSD(T)/CBS.It shows that theωB97M-V method is not only suitable for the study of the non-covalent interactions between the molecules of the main group elements,but also an excellent method for calculating the interaction energy between closed-shell transition metal complexes and fullerenes.We have screened out cost-effective and reliable DFT method for the theoretical study of the non-covalent interaction between phthalocyanine,porphyrin-based transition metal macrocyclic complexes and fullerenes.