Theoretical studies on CuF+, CuF, CuF−, CuF2, and CuF2−
Theoretical studies on CuF+, CuF, CuF−, CuF2, and CuF2−
复制标题
CuF+、CuF、CuF−、CuF2 和 CuF2− 的理论研究
DOI：
--
复制
发表时间：
1990
期刊：
影响因子：
--
通讯作者：
L. Aldridge
中科院分区：
文献类型：
--
作者：
P. Schwerdtfeger;P. Boyd;G. A. Bowmaker;L. Aldridge
用接近Hartree Fock（HF）极限质量的Cu和F基组进行了从头算SCF研究，以获得CuF+、CuF、CuF−、CuF 2和CuF 2 −分子基态性质的准确SCF结果，以及CuF 2的前两个低激发态。通过Møller-Plesset（MP）和组态相互作用（Cl）计算，研究了电子关联的影响.用一阶自旋轨道平均Pauli算符的耦合HF方法研究了相对论对CuF中~（63）Cu核四极耦合的影响。在HF水平下，63 Cu耦合常数被发现为35.8 MHz（e2 qQ h−1），而考虑到相对论，该值被降低到29.1 MHz，这与22.0 MHz的实验值更好地吻合。CuF的计算分子性质[re = 1.737 eV，De=4.38 eV，ωe = 562 cm−1（MP4）;re= 1.796 eV，De = 3.91 eV，ωe=585 cm−1（CISD）]与实验结果吻合良好（re = 1.745 eV，De = 4.43 eV，ωe=623 cm−1）。CuF+的绝热基态电势曲线避免了在两条离子电势曲线Cu+-F和Cu 2 +-F−之间的平衡距离附近交叉。在交叉点处，Cu和F电场梯度显示出尖锐的不连续性。
Ab initio SCF studies were performed with Cu and F basis sets of near-Hartree-Fock (HF) limit quality to obtain accurate SCF results for the molecular ground state properties of CuF+, CuF, CuF−, CuF2, and CuF2−, as well as for the first two low-lying excited states of CuF2. A study on the effects of electron correlation was carried out by Møller-Plesset (MP) and configuration interaction (Cl) calculations. The effect of relativity on the63Cu nuclear quadrupole coupling in CuF was determined by use of a coupled HF procedure for a first-order spin-orbital-averaged Pauli operator. At the HF level the63Cu coupling constant was found to be 35.8 MHz (in e2qQ h−1), while allowing for relativity the value was reduced to 29.1 MHz, which is in better agreement with the experimental value of 22.0 MHz. The calculated molecular properties for CuF [re = 1.737 Å,De=4.38 eV, ωe = 562 cm−1 (MP4);re= 1.796 Å,De = 3.91 eV,ωe=585 cm−1 (CISD)] were in good agreement with experiment (re = 1.745 Å,De = 4.43 eV,ωe=623 cm−1). The adiabatic ground-state potential curve of CuF+ avoids crossing near the equilibrium distance between the two ionic potential curves Cu+-F and Cu2+-F−. At the crossing point the Cu and F electric field gradients show a sharp discontinuity.