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在固态 NMR 中实现高效异核偶极去耦的核自旋哈密顿对称性的意义:超循环 rCW 方案的 Floquet 描述。

Significance of symmetry in the nuclear spin Hamiltonian for efficient heteronuclear dipolar decoupling in solid-state NMR: A Floquet description of supercycled rCW schemes.

机构信息

Center for Insoluble Protein Structures (inSPIN), Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark.

Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel.

出版信息

J Chem Phys. 2017 Mar 14;146(10):104202. doi: 10.1063/1.4977738.

Abstract

Symmetry plays an important role in the retention or annihilation of a desired interaction Hamiltonian in NMR experiments. Here, we explore the role of symmetry in the radio-frequency interaction frame Hamiltonian of the refocused-continuous-wave (rCW) pulse scheme that leads to efficient H heteronuclear decoupling in solid-state NMR. It is demonstrated that anti-periodic symmetry of single-spin operators (I, I, I) in the interaction frame can lead to complete annihilation of the H-H homonuclear dipolar coupling effects that induce line broadening in solid-state NMR experiments. This symmetry also plays a critical role in cancelling or minimizing the effect of H chemical-shift anisotropy in the effective Hamiltonian. An analytical description based on Floquet theory is presented here along with experimental evidences to understand the decoupling efficiency of supercycled (concatenated) rCW scheme.

摘要

对称性在 NMR 实验中保留或消除所需相互作用哈密顿量方面起着重要作用。在这里,我们探讨了在导致固态 NMR 中高效 H 异核去耦的重聚焦连续波 (rCW) 脉冲方案的射频相互作用框架哈密顿量中对称性的作用。结果表明,在相互作用框架中单自旋算符 (I, I, I) 的反周期对称性可以导致固态 NMR 实验中导致谱线展宽的 H-H 同核偶极耦合效应的完全消除。这种对称性在消除或最小化有效哈密顿量中 H 化学位移各向异性的影响方面也起着关键作用。本文提出了一种基于 Floquet 理论的解析描述,并结合实验证据来理解超循环(级联)rCW 方案的去耦效率。

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