铀酰叠氮离子化合物的质谱分析与理论计算  

Mass Spectrum and Theoretical Calculation for Azide Radical Complexes With Uranyl(Ⅴ)Cation[UO_(2)(N_(3))_(n)]+(n=1-4)

作　　者：洪静 韩昌财 费泽杰 唐圆圆 刘艳成[1] 周露露 刘洪涛[1] 熊孝根 董常武 HONG Jing;HAN Chang-cai;FEI Ze-jie;TANG Yuan-yuan;LIU Yan-cheng;ZHOU Lu-lu;LIU Hong-tao;XIONG Xiao-gen;DONG Chang-wu(Key Laboratory of Interfacial Physics and Technology,Shanghai Institute of Applied Physics,Chinese Academy of Sciences,Shanghai 201800,China;University of Chinese Academy of Sciences,Beijing 100049,China;School of Chemical Science and Engineering,Tongji University,Shanghai 200092,China;Shandong Energy Group Co,.LTD,Jinan 250101,China;Sino-French Institute of Nuclear Engineering and Technology,Sun Yat-sen University,Zhuhai 519082,China)

机构地区：[1]中国科学院上海应用物理研究所,上海201800 [2]中国科学院大学,北京100049 [3]同济大学化学科学与工程学院,上海200092 [4]山东能源集团有限公司,山东济南250101 [5]中山大学中法核工程与技术学院,广东珠海519082

出　　处：《核化学与放射化学》2023年第5期466-476,共11页Journal of Nuclear and Radiochemistry

基　　金：国家自然科学基金(22004128,22273121);中国科学院青年创新促进会基金(2021255);中国科学院上海应用物理研究所“育新计划”(E0553201);中国科学院战略性先导科技专项(XDA02020000);山东省重点研发计划(重大科技创新工程)(2020CXGC010402);广州市科技计划项目(202102080374)。

摘　　要：铀的多配位化学不仅在新型锕系化合物的结构研发中具有重要地位,也对环境和核废料处理问题产生重要影响。本研究报道了激光溅射U靶在N_(2)O载气中冷却膨胀生成[UO_(2)(N_(3))_(n)]+(n=0-4)的质谱结果,并结合理论计算对所生成离子的稳定结构和成键相互作用进行了分析。结果显示,N 3以自由基的形式与UO_(2)^(+)配位,且第一个N_(3)配体与UO_(2)^(+)存在成键相互作用。此外,进一步的定域化分子轨道分析表明,体系中存在多中心轨道离域。Coordination of uranium chemistry by multiligands has attracted attention as a way to obtain unique molecular structures and their possible use in environmental and nuclear waste disposal.In this work,mass spectrum with positive ions[UO_(2)(N_(3))_(n)]+(n=0-4)as the dominant peaks generated by laser evaporation of uranium target with N_(2)O as the carrier gas is reported.The associated quantitative calculations are carried out to explore structures and bonding interactions.The calculations show that N_(3)is bound to UO_(2)^(+)as a radical and reveal that the bonding interaction in the whole system is found only between the first N_(3)ligand and uranium atom.Further localized molecular orbital analyses indicate the presence of multi-centered orbital delocalization in the system.

关 键 词：锕系配位化学 铀酰化合物 计算化学 叠氮自由基化合物 

分 类 号：TL211.3[核科学技术—核燃料循环与材料] O657.63[理学—分析化学]