NiCO分子结构与解析势能函数  

The molecule structure and potential energy function of NiCO

作　　者：阮文[1,2] 胡强林[1] 谢安东[1] 余晓光[1] 朱正和[2] 

机构地区：[1]井冈山大学数理学院,吉安343009 [2]四川大学原子与分子物理研究所,成都610065

出　　处：《原子与分子物理学报》2010年第2期215-220,共6页Journal of Atomic and Molecular Physics

基　　金：国家自然科学基金(10965002,30960031,10676022);江西省教育厅科技研究项目(GJJ10540,2007326);江西省科技厅工业攻关项目(200621)

摘　　要：用密度泛函理论的B3P86方法,对镍原子采用LANL2DZ收缩价基,碳原子和氧原子采用6-311+G~*基组,对NiC、NiO和NiCO体系的结构进行优化,计算表明:NiC分子基态为~1∑^+态,键长为R_e=0.16070 nm,离解能为3.62948 eV.NiO分子基态的平衡核间距为0.16784 nm,其电子态为~3∑^-,离解能为3.45119 eV,拟合得到Murrell-Sorbie势能函数;NiCO分子有两个线性稳定构型,其中一个构型为Ni—C≡O(C_(∞υ)),电子态为~1∑^+,平衡核间距为R_(NiC)=0.16621 nm,R_(co)=0.11519 nm,离解能为12.80476 eV,另一个为Ni—O≡C(C_(∞υ)),电子态是~1∑^+,平衡核间距为R_(co)=0.11470 nm,R_(NiO)=0.17636 nm,离解能为11.24679 eV.由微观过程的可逆性原理分析了分子的可能的离解极限,并用多体展式理论导出基态NiCO分子的势能函数,其等势面图准确地再现了NiCO分子的结构特征和离解能,由此讨论了Ni+CO,NiC+O,NiO+C分子反应的势能面静态特征.Density functional theory （DFT） B3P86 have been used to calculate the equilibrium geometries and vibrational properties of the possible structures and electronic states of NiC, NiO and NiCO molecules with contracted valence basis set （LANL2DZ） for Ni atom and 6-311＋G for C and O atoms respectively. The present computational results predict that the ground electronic state of NiC is 1 ∑ ＋ with equilibrium geometry Rc=0. 16070 nm and the dissociation energy is 3. 62948 eV. Similarly, the ground electronic state of NiO is 3 ∑- with equilibrium geometry Re = 0. 16784 nm and the dissociation energy is 3. 45119 eV. The ground electronic state of Ni-C≡O is 1 ∑＋ （C∞v） with equilibrium geometries RNiC= 0. 16621 nm,Rco=0. 11519nm and the dissociation energy is 12. 80476 eV. At the same time, another metastable structure Ni--O≡C is found. Its equilibrium geometry and dissociation energy are Rco = 0. 11470 nm,RNiO =0. 17636 nm and 11. 24679 eV, respectively. Then, the analytic potential energy function of NiCO molecule is derived by many-body expansion theory for the first time. The contours of the potential energy surface are constructed, which clearly reproduce the character of the accurate structure and dissociation energy for NiCO. Furthermore, the molecular static reaction pathways based on this potential energy function are investigated.

关 键 词：NiCO 多体项展式理论 势能函数 

分 类 号：O561.1[理学—原子与分子物理]