任意简并电子态中的核磁共振化学位移。
NMR chemical shift in an electronic state with arbitrary degeneracy.
机构信息
School of Chemistry, University of Melbourne, VIC, Australia.
出版信息
Phys Rev Lett. 2012 Aug 17;109(7):073001. doi: 10.1103/PhysRevLett.109.073001. Epub 2012 Aug 16.
We present a theory of nuclear magnetic resonance shielding tensors for electronic states with arbitrary degeneracy. The shieldings are here expressed in terms of generalized Zeeman (g((k))) and hyperfine (A((k))) tensors, of all ranks k allowed by the size of degeneracy. Contrary to recent proposals [T. O. Pennanen and J. Vaara, Phys. Rev. Lett. 100, 133002 (2008)], our theory is valid in the strong spin-orbit coupling limit. Ab initio calculations for the fourfold degenerate Γ(8) ground state of lanthanide-doped fluorite crystals CaF(2):Ln (Ln=Pr(2+), Nd(3+), Sm(3+), and Dy(3+)) show that previously neglected contributions can account for more than 50% of the paramagnetic shift.
我们提出了一个任意简并电子态的核磁共振屏蔽张量理论。屏蔽张量在这里用广义塞曼（g((k)))和超精细（A((k)))张量表示，其阶数 k 由简并度的大小决定。与最近的提议相反[T. O. Pennanen 和 J. Vaara, Phys. Rev. Lett. 100, 133002 (2008)]，我们的理论在强自旋轨道耦合极限下是有效的。对于镧系掺杂萤石晶体 CaF(2):Ln（Ln=Pr(2+)、Nd(3+)、Sm(3+)和 Dy(3+)）的四重简并Γ(8)基态的从头算计算表明，以前被忽略的贡献可以解释超过 50%的顺磁位移。
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