IIB族元素同核二聚物的电子基态和低激发态势能曲线的高精度计算研究

项目名称： IIB族元素同核二聚物的电子基态和低激发态势能曲线的高精度计算研究

项目编号： No.21503153

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 涂喆研

作者单位： 西安工程大学

项目金额： 21万元

中文摘要： 本项目用耦合簇理论(CC)和运动方程耦合簇理论(EOM-CC)，结合四阶多项式拟合方法研究Zn2、Cd2和Hg2的电子基态和低激发态的势能曲线、光谱常数以及吸收、发射光谱。所有理论计算均建立在二分量相对论有效势(2c-RECP)和与之匹配的高级别基函数的基础上。对基态，我们用含自旋轨道耦合(SOC)的SOC-CCSDT方法进行研究。对激发态，我们用两种方法分别计算其SOC效应：(1)用不含SOC的EOM-CCSDT方法计算得到不含SOC的激发态，再用含SOC的EOM-SOC-CCSD方法计算激发态的SOC分裂情况，进而得到含SOC的激发态。(2)用不含SOC的EOM-CCSD方法和含SOC的EOM-SOC-CCSD方法构建起电子态间的有效SOC矩阵，再将其放到不含SOC的EOM-CCSDT计算中得到含SOC的激发态。本项目的计算结果可为将来的实验和理论研究提供可靠的理论依据。

中文关键词： 自旋轨道耦合；电子激发态；势能曲线；耦合簇理论；IIB族元素同核二聚物

英文摘要： In this work, coupled-cluster theory and equation-of-motion coupled-cluster theory combined with fourth order polynomial fitting are used to study the potential energy curves, spectroscopic constants and absorption/emission spectrum of electronic ground and low-lying excited states for Zn2, Cd2 and Hg2. All the theoretical calculations in this work are based on the two-component relativistic effective core potential and the matched high-level basis sets. For the ground states, the SOC-CCSDT method including spin-orbit coupling (SOC) is used to study it. For the low-lying excited states, two approaches are used to study the spin-orbit coupling, respectively: (1)The EOM-CCSDT method without SOC is used to calculate the excited states without SOC, then the EOM-SOC-CCSD method including SOC is used to calculate the spin-orbit coupling splitting of excited states, the excited states including SOC are obtained at last. (2)Both the EOM-CCSD method without SOC and the EOM-SOC-CCSD method including SOC are used to establish the.effective SOC matrices between electronic states, and then the SOC matrices are put into the EOM-CCSDT calculations without SOC to obtain the excited states including SOC at last. The theoretical results in this work will provide reliable theoretical references for the future experimental and theoretical studies.

英文关键词： spin-orbit coupling;electronic excited states;potential energy curves;coupled-cluster theory;group 12 homonuclear dimers