ZrF分子基态(X^2Δ)的光谱研究

Study on spectrum for the ground state(X^2Δ) of ZrF molecule

现有Zr F分子的理论值与实验值偏差较大,且有一些光谱参数暂时还没有实验结果.本文基于群论及原子分子反应静力学推导出了Zr F分子的基态电子状态(X2Δ)和合理的离解极限.采用密度泛函理论(B3LYP,B3P86)和二阶微扰理论(MP2)方法,对Zr和F原子分别选择不同的基组进行结构优化和频率计算,根据计算结果及现有实验数据,分析得出在MP2方法下,对Zr使用Lan L2DZ基组,对F使用AUG-cc-PVTZ基组计算得出的结构与实验值较为符合.然后根据优化后的方法及基组扫描了基态Zr F分子的单点能,得到的基态Zr F分子的势能曲线数值,通过Level 8.0软件拟合了势能曲线并得出了一些光谱常数.最后,由拟合得到的光谱常数(De,ωe,ωeχe,Te,Be)与实验值和其他理论值进行了比较.本文的计算结果(Re=0.1859nm,De=7.1046e V,ωe=701.25cm-1,ωeχe=2.6398cm-1,Te=-9.3473cm-1,Be=0.3104cm-1)更接近于实验值.

The existing theoretical and experimental values of ZrF molecule deviate significantly , and some spec-tral parameters have no experimental values temporarily .In this paper , based on the group theory and the atomic and molecular reaction statics , the reasonable dissociation limits and the ground state （ X2Δ） for ZrF molecule have been derived .Zr and F atoms respectively select different basis sets to make structural optimization and fre-quency calculation with density functional theory （ B3LYP, B3P86 ） and second -order perturbation theory （MP2） methods.According to the computed results and the existing experimental values , we find that by using MP2 methods , the structures derived from the MP 2 calculation are fairly consisted with the experimental values through the LanL2DZ basis sets for Zr atom and the AUG -cc-PVTZ basis sets for F atom .Then the potential energy curve of the ground states of ZrF molecule is scanned by the Mp 2/LanL2DZ/AUG-cc-PVTZ level of theory, and level 8.0 software is used to fit the potential energy curve .At last, the spectroscopy constants （De,ωe , ωeχe , Te , Be ） related to the potential energy curve are calculated and compared with the existing theoretical and experimental values .The calculated results of this paper （ Re =0.1859nm, De =7.1046eV, ωe =701.25cm-1 ,ωeχe =2.6398cm -1 , Te =-9.3473cm-1 , Be =0.3104cm -1 ） are closer to the experimental val-ues .