Bengs Christian
School of Chemistry, Southampton University, University Road, SO17 1BJ, UK.
J Magn Reson. 2021 Jan;322:106868. doi: 10.1016/j.jmr.2020.106868. Epub 2020 Nov 6.
Nuclear Magnetic Resonance (NMR) experiments involve coherent and incoherent dynamics. Incoherent dynamics give rise to nuclear spin relaxation typically accounted for by a differential equation known as a quantum master equation. Out of the existing master equations the Lindblad equation is particularly important. A central theorem of open quantum theory states that a relaxation process represents a quantum Markovian process if and only if it can be described by a Lindblad master equation. This in turn raises serious questions regarding the compatibility of conventional NMR relaxation theory and one of the most fundamental results of open quantum theory. The NMR treatment of important Markovian relaxation mechanisms such as Brownian motion or chemical exchange events do in general not result in a master equation in Lindblad form and would therefore be at odds with the mathematically rigorous theory of open quantum systems. We explore this apparent conflict for two important chemical exchange phenomena and show that their conventional treatment may be recast into a suitable Lindblad equation. Similarities between spatial diffusion and multi-site exchange events allow us to extend our results to nuclear spin relaxation due to translational diffusion. As a result we are able to show that the NMR treatment of intramolecular exchange and translational diffusion represent valid quantum Markovian processes compatible with the rigorous definitions of open quantum theory.
核磁共振(NMR)实验涉及相干和非相干动力学。非相干动力学导致核自旋弛豫,通常由一个称为量子主方程的微分方程来描述。在现有的主方程中,林德布拉德方程尤为重要。开放量子理论的一个核心定理表明,一个弛豫过程当且仅当它可以由林德布拉德主方程描述时,才代表一个量子马尔可夫过程。这反过来又引发了关于传统NMR弛豫理论与开放量子理论最基本结果之一的兼容性的严重问题。对于重要的马尔可夫弛豫机制,如布朗运动或化学交换事件,NMR处理通常不会得到林德布拉德形式的主方程,因此与开放量子系统的数学严格理论不一致。我们针对两种重要的化学交换现象探讨了这一明显的冲突,并表明它们的传统处理方式可以被改写为一个合适的林德布拉德方程。空间扩散和多位点交换事件之间的相似性使我们能够将结果扩展到由于平移扩散引起的核自旋弛豫。结果,我们能够表明,分子内交换和平移扩散的NMR处理代表了与开放量子理论的严格定义兼容的有效的量子马尔可夫过程。