The speciation and mobility of actinide complexes in the environment depend strongly on ligand concentration.It is therefore important to understand the structural,bonding properties of actinide compounds.In this work,a series of plutonyl(Ⅴ,Ⅵ)complexes,including aquo,plutonyl nitrate complexes,carbonate,hydroxo,and plutonium fluoride complexes are investigated on the base of DFT in conjunction with relativistic effect core potential(RECP)or all-electron basis set in Zero-order regular approximation(ZORA)framework.The structures in gaseous and aqueous are obtained and compared with available experiments.The QTAIM and NCI are utilized to analyze the bonding natures of studied complexes.The relative stabilities between plutonyl(Ⅴ)and(Ⅵ)can be well reflected in chemical bonding analyses.The weak interaction between plutonyl and other ligands,H2O,NO3,CO3,F/Cl/Br,OH can not be appropriately described by QTAIM method,whereas the NCI method can successfully identify the interaction characteristics.The detailed interaction sequences are given for studied ligands.