Comparative DFT Study of [Mg(CHZ)_3](ClO_4)_2 and [Mg(CHZ)_3](NO_3)_2(CHZ=Carbohydrazide)  

作　　者：聂西度 黄辉胜 

机构地区：[1]School of Chemistry and Chemical Engineering,Central South University [2]Department of Material and Chemical Engineering,Hunan Institute of Technology [3]College of Chemistry and Chemical Engineering,Yangtze Normal University

出　　处：《Journal of Wuhan University of Technology(Materials Science)》2012年第4期679-683,共5页武汉理工大学学报（材料科学英文版）

基　　金：Funded by the National Natural Science Foundation of China(No. 21075138);the Natural Science Foundation of Chongqing Province, China(No.cstc2011jjA50013,No.cstc2011jjA0780);the Education Commission of Chongqing City of China(KJ121311)

摘　　要：The molecular geometry,electronic structure,thermochemistry and infrared spectra of [Mg（CHZ）3]（ClO4）2 and [Mg（CHZ）3]（NO3）2 were comparatively studied using the Heyd-Scuseria-Ernzerhof（HSE） screened hybrid density functional with 6-31G＊＊ basis set.The experimental results show that the complexes have six-coordinated octahedron feature,and the metal-ligand interactions are predominantly ionic in nature.The calculated heats of formation predict that [Mg（CHZ）3]（NO3）2 is more stable than [Mg（CHZ）3]（ClO4）2.Detailed NBO analyses indicate that the ligand-anion interaction plays an important role in the stability for these two energetic complexes.Moreover,the stretching vibration frequencies of N-H bonds shift to lower wave number compared to the free CHZ ligand,which are caused by the delocalizations from N-H bond orbital to lone-pair electron antibond orbital of magnesium.The molecular geometry,electronic structure,thermochemistry and infrared spectra of [Mg（CHZ）3]（ClO4）2 and [Mg（CHZ）3]（NO3）2 were comparatively studied using the Heyd-Scuseria-Ernzerhof（HSE） screened hybrid density functional with 6-31G＊＊ basis set.The experimental results show that the complexes have six-coordinated octahedron feature,and the metal-ligand interactions are predominantly ionic in nature.The calculated heats of formation predict that [Mg（CHZ）3]（NO3）2 is more stable than [Mg（CHZ）3]（ClO4）2.Detailed NBO analyses indicate that the ligand-anion interaction plays an important role in the stability for these two energetic complexes.Moreover,the stretching vibration frequencies of N-H bonds shift to lower wave number compared to the free CHZ ligand,which are caused by the delocalizations from N-H bond orbital to lone-pair electron antibond orbital of magnesium.

关 键 词：energetic complex carbohydrazide density functional theory electronic structure heats of formation 

分 类 号：O627.21[理学—有机化学]