论文标题

通过对广义Hartree-fock状态的自旋取向来计算分子G调节器

Calculation of molecular g-tensors by sampling spin orientations of generalised Hartree-Fock states

论文作者

Tabrizi, Shadan Ghassemi, Rodríguez-Guzmán, R., Jiménez-Hoyos, Carlos A.

论文摘要

自旋轨道耦合在自一致场(SCF)计算中的变异包含需要一个广义的两个组件框架,这允许单确定波函数完全破坏自旋对称性。分子G量的各个组件通常是从单独的SCF溶液中获得的,这些溶液将沿三个主张量轴之一对齐的磁矩对齐。但是,该策略提出了一个问题,即解决方案之间的能量差异是否相关,或者如果不通过分子对称性确定主轴系统,则如何达到融合。目前的工作通过类似于发电机坐标方法(GCM)的简单两步过程解决了这些问题。首先,一些广义的Hartree Fock(GHF)溶液会收敛,在需要的情况下施加对磁性或自旋载体的方向的约束。然后,通过非正交构型相互作用形成GHF决定因素的叠加。该过程产生了一个Kramers Doublet,以计算完整的G量。另外,对于具有较弱的自旋轨道效应的系统,单个GHF决定因素的自旋旋转跨越基础上的对角线化可以通过消除与自旋污染相关的误差来定性正确的G量。对于小的第一行分子,根据实验数据和完整的构型相互作用结果评估了这些方法。进一步证明了两个系统(一个虚拟的四面体CH4+物种和CUF4(2-)复合物),与替代性均值野外方法相反,GCM策略可以正确地描述牙制偏度基层的旋转轨道分裂,从而导致较大的g速度和g-Shifts,并可能导致g-shift g-shifts且可能导致负值G-Values。

The variational inclusion of spin-orbit coupling in self-consistent field (SCF) calculations requires a generalised two-component framework, which permits the single-determinant wave function to completely break spin symmetry. The individual components of the molecular g-tensor are commonly obtained from separate SCF solutions that align the magnetic moment along one of the three principal tensor axes. However, this strategy raises the question if energy differences between solutions are relevant, or how convergence is achieved if the principal axis system is not determined by molecular symmetry. The present work resolves these issues by a simple two-step procedure akin to the generator coordinate method (GCM). First, a few generalised Hartree Fock (GHF) solutions are converged, applying, where needed, a constraint to the orientation of the magnetic-moment or spin vector. Then, superpositions of GHF determinants are formed through non-orthogonal configuration interaction. This procedure yields a Kramers doublet for the calculation of the complete g-tensor. Alternatively, for systems with weak spin-orbit effects, diagonalisation in a basis spanned by spin rotations of a single GHF determinant affords qualitatively correct g-tensors by eliminating errors related to spin contamination. For small first-row molecules, these approaches are evaluated against experimental data and full configuration interaction results. It is further demonstrated for two systems (a fictitious tetrahedral CH4+ species, and a CuF4(2-) complex) that a GCM strategy, in contrast to alternative mean-field methods, can correctly describe the spin-orbit splitting of orbitally-degenerate ground states, which causes large g-shifts and may lead to negative g-values.

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