We investigate the ability of mechanical and electronic density functional theory‐based embedding approaches to describe the solvent effects on nuclear magnetic resonance (NMR) shielding constants of the 95Mo nucleus in the molybdate ion in aqueous solution. From the description obtained from calculations with two‐ and four‐component relativistic Hamiltonians, we find that, for such systems, spin‐orbit coupling effects are clearly important for absolute shielding values, but for relative quantities, a scalar relativistic treatment provides sufficient estimation of the solvent effects. We find that the electronic contributions to the solvent effects are relatively modest yet decisive to provide a more accurate magnetic response of the system when compared to reference supermolecular calculations. We analyze the errors in the embedding calculations by statistical methods, as well as through a real‐space representation of NMR shielding densities, which are shown to provide a clear picture of the physical processes at play.

中文翻译：

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使用相对论嵌入研究溶剂对钼酸盐离子 (MoO42−) 磁性的影响

我们研究了基于机械和电子密度泛函理论的嵌入方法的能力，以描述溶剂对水溶液中钼酸盐离子中 95Mo 核的核磁共振 (NMR) 屏蔽常数的影响。从用二分量和四分量相对论哈密顿量计算得到的描述中，我们发现，对于这样的系统，自旋轨道耦合效应对于绝对屏蔽值显然很重要，但对于相对量，标量相对论处理提供了足够的估计溶剂效应。我们发现，与参考超分子计算相比，对溶剂效应的电子贡献相对适中，但对于提供更准确的系统磁响应具有决定性意义。