National High Magnetic Field Laboratory, Florida State University, 1800 E. Paul Dirac Dr, FL 32310, USA.
J Magn Reson. 2021 Dec;333:107106. doi: 10.1016/j.jmr.2021.107106. Epub 2021 Nov 9.
Numerical simulations of Magic Angle Spinning Dynamic Nuclear Polarization (MAS-DNP) have transformed the way the DNP process is understood in rotating samples. In 2012, two methods were concomitantly developed to simulate small spin systems (< 4 spin-1/2). The development of new polarizing agents, including those containing metal centers with S > 1/2, makes it necessary to further expand the numerical tools with minimal approximations that will help rationalize the experimental observations and build approximate models. In this paper, three strategies developed in the past five years are presented: an adaptive integration scheme, a hybrid Hilbert/Liouville formalism, and a method to truncate the Liouville space basis for periodic Hamiltonian. Each of these methods enable time savings ranging from a factor of 3 to > 100. We illustrate the code performance by reporting for the first time the MAS-DNP field profiles for "AMUPol", in which the couplings to the nitrogen nuclei are explicitly considered, as well as Cross-Effect MAS-DNP field profiles with two electrons spin 5/2 interacting with a nuclear spin 1/2.
数值模拟魔角旋转动态核极化(MAS-DNP)改变了人们对旋转样品中 DNP 过程的理解方式。2012 年,同时开发了两种方法来模拟小自旋系统(<4 个自旋-1/2)。新型极化剂的发展,包括那些含有 S>1/2 的金属中心的极化剂,使得有必要进一步扩展数值工具,以最小的近似值帮助合理化实验观察并构建近似模型。在本文中,介绍了过去五年开发的三种策略:自适应积分方案、混合 Hilbert/Liouville 形式和用于周期性哈密顿截断 Liouville 空间基的方法。这些方法中的每一种都可以节省 3 到>100 倍的时间。通过首次报告“AMUPol”的 MAS-DNP 场分布来说明代码性能,其中明确考虑了与氮核的耦合,以及两个电子自旋 5/2 与核自旋 1/2 相互作用的交叉效应 MAS-DNP 场分布。