论文标题
主动空间和非正交构型相互作用方法用于研究金属表面上的分子
Active Spaces and Non-Orthogonal Configuration Interaction Approaches for Investigating Molecules on Metal Surfaces
论文作者
论文摘要
我们测试了一组多构型波函数方法，用于计算代表金属表面上一个分子的两点安德森模型的基态电子总体。特别是，我们比较了（i）一个像波函数一样的hartree fock，其中允许边缘轨道是非正交的，而（ii）基于约束的hartree-fock状态的完全非正交构型相互作用波函数。我们测试了强和弱的金属分子杂交（$γ$）的限制，以及强和弱电子电阻（U）限制。与精确的数值重归其化组（NRG）理论相比，我们获得了准确的结果，在适当的情况下恢复了电荷转移状态。当前的框架应为在金属表面上运行分子非绝热动态的路径。
We test a set of multiconfigurational wavefunction approaches for calculating the ground state electron population for a two-site Anderson model representing a molecule on a metal surface. In particular, we compare (i) a Hartree Fock like wavefunction where frontier orbitals are allowed to be nonorthogonal versus (ii) a fully non-orthogonal configuration interaction wavefunction based on constrained Hartree-Fock states. We test both the strong and weak metal-molecule hybridization ($Γ$) limits as well as the strong and weak electron-electron repulsion (U) limits. We obtain accurate results as compared with exact numerical renormalization group (NRG) theory, recovering charge transfer states where appropriate. The current framework should open a path to run molecular non-adiabatic dynamics on metal surfaces.
