Density functional calculations are used to determine structural and electronic properties of P4,P4O6,P4O10,P20O30 and P20O50 clusters and their protonated derivatives.These oxygen-rich phosphorus oxides are predicted to have relatively high stabilities with respect to their components P4 and O2,and their unsaturated P and end-on O atoms as the proton acceptor can accommodate multiple protons to generate highly positively charged cationic clusters,such as P20O30H1010+.Calculations indicate that P4O6 and P20O30 have higher reactivity toward the proton capture than the P4,P4O10 and P20O50 clusters,and the most stable protonated clusters among these different series of cationic clusters are P4H22+,P4O6H22+,P4O10H33+,P20O30H44+ and P20O50H44+,respectively.The cage skeleton of the phosphorus oxide clusters shows high stability for the consecutive protonation,and the unsymmetrical stretching of the skeletal P-O bond and the wagging mode of P-H coupled with the P-O bond stretching have strong adsorptions.These computational findings are useful for further experimental and theoretical studies of novel phosphorus oxide clusters and their highly positively charged derivatives.