团簇Co4P的热力学稳定性及电子性质

Thermodynamic Stability and Electronic Properties of Cluster Co4P

运用密度泛函理论,对团簇Co4P在B3LYP/Lanl2dz水平下进行全参数优化和频率验证,排除含虚频和相同的构型后,最终得出6种稳定的优化构型,其中构型1(2)最为稳定;各构型的能量由低到高依次为1(2)<1(4)<2(2)<2(4)<3(2)<3(4),且各构型的热力学稳定性相差不大;团簇Co4P的电子转移方向为P→Co;各优化构型电子转移能力的大小关系为3(4)>2(2)>3(2)>1(4)>1(2)>2(4);团簇Co4P大部分电子的流向是由P-3p轨道和Co-4s轨道流向Co-3d轨道;Co-4s轨道与Co-3d、Co-4p轨道的布居数同时存在拮抗作用,Co-3d和Co-4p轨道的布居数存在协同作用;各构型轨道布居数变化量的波动范围较小。

Based on the density functional theory,the whole parameter optimization and frequency verification of cluster Co4P were carried out under the B3LYP/Lanl2dz level.After eliminating the imaginary frequency and the same configurations,six stable optimized configurations were finally obtained,among which configuration 1(2)is the most stable one;the order of energy of each configuration is 1(2)<1(4)<2(2)<2(4)<3(2)<3(4),and the thermodynamics of each configuration is stable;the electron transfer direction of Co4P is P→Co,and the relationship between the electron transfer ability of each optimized configuration is 3(4)>2(2)>3(2)>1(4)>1(2)>2(4);most of the electrons flow direction of Co4P is from P-3p orbital and Co-4s orbital to Co-3d orbital;and the Co-4s orbital and Co-3d,Co-4p orbital have antagonistic effect at the same time,the population of Co-3d orbital and Co-4p has a synergistic effect,and the variation range of the population of each configuration orbital is relatively stable.