计算化学在金属配合物磁化率测定实验教学中的应用  

Application of Computational Chemistry in the Determination of Magnetic Susceptibility of Metal Complexes

作　　者：吴红 王钰熙 冯红艳[1] 王晓葵[1] 金邦坤[1] 雷璇 吴强华[1] 李红春[1] Hong Wu;Yuxi Wang;Hongyan Feng;Xiaokui Wang;Bangkun Jin;Xuan Lei;Qianghua Wu;Hongchun Li(National Demonstration Center for Experimental Chemistry Education(University of Science and Technology of China),Hefei 230026,China;School of Flexible Electronics,SunYat-Sen University,Shenzhen 518107,Guangdong Province,China)

机构地区：[1]化学国家级实验教学示范中心(中国科学技术大学),合肥230026 [2]中山大学柔性电子学院,广东深圳518107

出　　处：《大学化学》2025年第3期116-123,共8页University Chemistry

基　　金：安徽省教学研究项目(2022jyxm1801);中国科学技术大学本科质量工程项目(2022xjyxm022,2023xjyxm044,2024xjyxm045)。

摘　　要：金属配合物磁化率测定是经典的大学物理化学实验,一般通过古埃磁天平测定配合物磁化率,进而确定配合物中心离子的电子结构,与晶体场理论知识紧密联系。为让学生直观理解电子结构对配合物微观结构和结构稳定性的影响,深入理解实验内容,在传统磁化率测定实验基础上引入计算化学方法,采用Gaussian计算软件分别对FeSO_(4)·7H_(2)O和K_(4)Fe(CN)_(6)·3H_(2)O的中心离子的高、低自旋电子结构进行计算,将抽象、复杂的电子排布的影响具象化到能量和键长的比较,能量低的对应为有利的自旋状态,并将计算优化得到的几何结构与单晶X射线衍射结构数据进行比较,进一步确定有利的自旋状态。本实验以计算为桥梁,将实验测定结果、计算结果与理论知识有机结合起来,有助于培养学生实验结合理论、宏观联系微观的思维方式。同时利于激发高年级本科生的实验兴趣,提高综合实验技能。Magnetic susceptibility measurement of metal complexes is a classic experiment in undergraduate physical chemistry courses,traditionally performed using a Gouy magnetic balance to determine the electron configuration of the central ion.This process is closely related to the theoretical framework of crystal field theory.To enhance students’understanding of the impact of electronic structure on the the microstructure and stability of the complexes,computational chemistry methods have been integrated into this experiment.Using Gaussian software,the high-spin and low-spin electronic configurations of the central ions in FeSO_(4)·7H_(2)O and K_(4)Fe(CN)_(6)·3H_(2)O were calculated.This approach transforms the abstract and complex concept of electronic arrangements into a tangible comparison of energy and bond length,where the lower energy configuration corresponds to the more favorable spin state.Additionally,the optimized geometries from the calculations were compared with single-crystal X-ray diffraction data to validate the stable structures.By bridging experimental results,computational findings,and theoretical knowledge,this improved experiment cultivates students'ability to integrate experimental and theoretical approaches and to connect macroscopic observations with microscopic insights.Furthermore,it inspires senior undergraduates to engage more deeply in experimentation and enhances their comprehensive experimental skills.

关 键 词：晶体场理论 金属配合物 古埃法 量化计算 实验改进 

分 类 号：G64[文化科学—高等教育学] O6[文化科学—教育学]