Unified Description of Proton NMR Relaxation in Water, Acetonitrile, and Methane from Molecular Dynamics Simulations in the Liquid, Supercritical, and Gas Phases
Unified Description of Proton NMR Relaxation in Water, Acetonitrile, and Methane from Molecular Dynamics Simulations in the Liquid, Supercritical, and Gas Phases
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DOI：
10.1021/acs.jpcb.2c06411
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发表时间：
2023-01-26
影响因子：
3.3
通讯作者：
Philips，Adam
中科院分区：
文献类型：
--
作者：
Autschbach，Jochen;Philips，Adam
通过从头算和基于力场的分子动力学模拟，对水、乙腈和甲烷中大范围相图的质子核磁共振弛豫进行了综合计算。用于自旋旋转(SR)对驰豫贡献的公式是为任何分子对称性而发展的，并且利用了全分子SR张量，这些张量是通过Kohn-Sham(KS)密度泛函从第一原理计算出来的。结合偶极贡献的计算，获得了与测量的总弛豫速率近乎定量的一致。
A comprehensive calculation of proton NMR relaxation in water, acetonitrile, and methane across a wide range of the phase diagram is provided via ab initio and force-field-based molecular dynamics simulations. The formalism used for the spin-rotation (SR) contribution to relaxation is developed for use with any molecular symmetry and utilizes the full molecular SR tensors, which are calculated from first-principles via Kohn–Sham (KS) DFT. In combination with calculations of the dipolar contribution, near-quantitative agreement with total measured relaxation rates is achieved.