Mudgil Manjeet, Kurur Narayanan D
Chemistry Department, Indian Institute of Technology Delhi, New Delhi 110016, India.
Phys Chem Chem Phys. 2024 Jul 24;26(29):19908-19920. doi: 10.1039/d4cp01995d.
Over the last two decades, numerous pulse sequences have been introduced for the excitation of long-lived spin order (LLS) in high fields. The long continuous wave (CW) or adiabatic pulses used in the SLIC and APSOC sequences should remind one of the spin-locking pulses that are used to induce cross-polarization (CP). Dynamics during these spin-lockings in CP experiments are explained through a geometrical formalism. However, the SLIC and APSOC sequences are described in terms of the energy-level picture or in the language of level anti-crossings. Motivated by this analogy, this work presents here a geometrical formalism for the LLS excitation by spin-locking pulses in weakly coupled systems. The formalism is similar to the one used for CP dynamics and reveals new pulse sequences involving CW or adiabatic locking. A similar formalism for the sustaining period of LLS is also provided, which reveals new features of the dynamics and suggests the usage of modulated spin-lockings for proper LLS sustaining. For strong and intermediate regimes, although a simple geometrical formalism seems infeasible, a new pulse sequence that employs a ramp-down adiabatic pulse for both LLS excitation and reconversion to observables in both these regimes is presented here. Given the similarities between LLS excitation and well-developed CP, it may be anticipated that this work would initiate the search for new LLS excitation methods and applications.
在过去二十年中,已经引入了许多脉冲序列用于在高场中激发长寿命自旋序(LLS)。SLIC和APSOC序列中使用的长连续波(CW)或绝热脉冲应会让人联想到用于诱导交叉极化(CP)的自旋锁定脉冲。CP实验中这些自旋锁定过程中的动力学通过几何形式来解释。然而,SLIC和APSOC序列是根据能级图或能级反交叉的语言来描述的。受此类比的启发,本文提出了一种用于弱耦合系统中通过自旋锁定脉冲激发LLS的几何形式。该形式与用于CP动力学的形式相似,并揭示了涉及CW或绝热锁定的新脉冲序列。还提供了一种用于LLS维持期的类似形式,它揭示了动力学的新特征,并建议使用调制自旋锁定来适当维持LLS。对于强场和中场区域,尽管简单的几何形式似乎不可行,但本文在此提出了一种新的脉冲序列,该序列在这两种区域中均采用斜坡下降绝热脉冲来进行LLS激发和转换为可观测信号。鉴于LLS激发与成熟的CP之间的相似性,可以预期这项工作将引发对新的LLS激发方法和应用的探索。