Identification of a Reliable DFT Calculation Method to Predict the Ground-and Excited-State Properties of Nickel(Ⅱ) Complexes with Porphyrin in Crude Oil  

作　　者：Pu Ning Ren Qiang Hu Dawei Fang Wei Yang Qinghe Wang Zhen Hu Anpeng Xu Lei Ge Xin 

机构地区：[1]SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083,China [2]Institute of Nuclear Agricultural Sciences,Key Laboratory of Nuclear Agricultural Sciences of Ministry of Agriculture and Zhejiang Province,Zhejiang University,Hangzhou 310058,China [3]SINOPEC Geophysical Research Institute,Nanjing 211103,China

出　　处：《China Petroleum Processing & Petrochemical Technology》2023年第4期106-116,共11页中国炼油与石油化工（英文版）

基　　金：supported by National Key R & D program of China (No.2021YFA1501204);Contract Projects of China Petroleum & Chemical Corporation (SINOPEC Corp.) (grant number 123017;grant number 121043-2)。

摘　　要：Metalloporphyrins have devastating effects on the deep processing and efficient utilization of petroleum resources. Various porphyrins are derived from porphin by substitution at the β, meso, or both positions. Herein, we focus on the interaction between nickel(Ⅱ) and the porphyrin skeleton. Five different density functionals were selected for determining a reliable approach to simulate porphyrin-nickel(Ⅱ) complexes. At D4h symmetry, the 10b1g, 15a1g, 4e1g and 9b2g were dominated by the 3d character of nickel. Compared with pure density functional, the hybrid functional gave larger highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) gap, and the higher HOMO-LUMO gap also corresponded to a higher excitation energy. The characteristic Soret and Q bands modeled by timedependent density functional theory(TDDFT) calculations matched well with experimental results, and the absorption was discussed in detail with natural transition orbitals(NTO) analysis. Furthermore, the binding character of nickel(Ⅱ) with various substituted porphyrins were calculated at perdew-burke-ernzerhof(PBE) level, showed that the geometry and complexation behavior of porphyrin-nickel(Ⅱ) complexes could be significantly tuned by different substituents. The symmetry of the complex was reduced and the skeleton ring get distortion when introducing different substituents. Compared with ETIO porphyrin, the introduction of phenyl on the β position can expand the conjugated system and promote the covalent character of Ni-N bond.

关 键 词：porphyrin-nickel(Ⅱ) DFT/TDDFT binding character spectroscopic properties substituent effect 

分 类 号：TE622[石油与天然气工程—油气加工工程]