Do Models beyond Hybrid Density Functionals Increase the Agreement with Experiment for Predicted NMR Chemical Shifts or Electric Field Gradient Tensors in Organic Solids?
Do Models beyond Hybrid Density Functionals Increase the Agreement with Experiment for Predicted NMR Chemical Shifts or Electric Field Gradient Tensors in Organic Solids?
复制标题
混合密度泛函之外的模型是否会增加与有机固体中预测的 NMR 化学位移或电场梯度张量实验的一致性？
DOI：
10.1021/acs.jpca.2c07657
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Beran, Gregory J.
中科院分区：
文献类型：
--
作者：
Iuliucci, Robbie J.;Hartman, Joshua D.;Beran, Gregory J.
化学位移和电场梯度（EFG）张量分量的从头算预测经常用于帮助解释固态核磁共振（NMR）实验。通常情况下，这些预测采用密度泛函理论（DFT）与广义梯度近似（GGA）泛函，虽然混合泛函已被证明可以提高相对于实验的准确性。在这里，我们检查了GGA近似之外的十几个模型的性能来预测固态NMR可观测量，包括元GGA、混合和双混合密度泛函以及二阶Møller-Plesset微扰理论（MP2）。这些模型进行了测试的有机分子晶体数据集包含169个实验13 C和15 N化学位移和11417 O和14 N EFG张量分量。为了使这些计算负担得起，规范，包括投影仪增广波（GIPAW）Perdew-Burke-Ernzerhof（PBE）计算周期性边界条件相结合的局部分子内校正计算在更高的理论水平。在对静态DFT优化的晶体结构进行的典型NMR性质计算的背景下，基准测试发现，双混合DFT泛函产生的误差与实验相比，在最佳情况下不小于混合泛函的误差，并且它们可以更大。MP2与实验的误差甚至更大。总的来说，没有实际的优势，发现使用任何测试的双杂化泛函或MP2预测实验固态NMR化学位移和EFG张量组件的常规有机晶体，特别是考虑到这些方法的较高的计算成本。这一发现可能反映了有利于混合泛函的误差消除。相对于实验，提高预测的化学位移和EFG张量的准确性可能需要对晶体结构、其动力学和其他因素进行更稳健的处理。
Ab initiopredictions of chemical shifts and electric field gradient (EFG) tensor components are frequently used to help interpret solid-state nuclear magnetic resonance (NMR) experiments. Typically, these predictions employ density functional theory (DFT) with generalized gradient approximation (GGA) functionals, though hybrid functionals have been shown to improve accuracy relative to experiment. Here, the performance of a dozen models beyond the GGA approximation are examined for the prediction of solid-state NMR observables, including meta-GGA, hybrid, and double-hybrid density functionals and second-order Møller–Plesset perturbation theory (MP2). These models are tested on organic molecular crystal data sets containing 169 experimental13C and15N chemical shifts and 11417O and14N EFG tensor components. To make these calculations affordable, gauge-including projector augmented wave (GIPAW) Perdew–Burke–Ernzerhof (PBE) calculations with periodic boundary conditions are combined with a local intramolecular correction computed at the higher level of theory. Within the context of typical NMR property calculations performed on a static, DFT-optimized crystal structure, the benchmarking finds that the double-hybrid DFT functionals produce errors versus experiment that are no smaller than those of hybrid functionals in the best cases, and they can be larger. MP2 errors versus experiment are even bigger. Overall, no practical advantages are found for using any of the tested double-hybrid functionals or MP2 to predict experimental solid-state NMR chemical shifts and EFG tensor components for routine organic crystals, especially given the higher computational cost of those methods. This finding likely reflects error cancellation benefiting the hybrid functionals. Improving the accuracy of the predicted chemical shifts and EFG tensors relative to experiment would probably require more robust treatments of the crystal structures, their dynamics, and other factors.
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影响因子：
5.5
作者：
Hartman JD;Mathews A;Harper JK
通讯作者：
Harper JK
影响因子：
5.6
作者：
Gao, Peng;Zhang, Jun;Glezakou, Vassiliki-Alexandra
通讯作者：
Glezakou, Vassiliki-Alexandra
使用 DFT 计算建模的 A 型西咪替丁的化学位移张量：对 NMR 晶体学的影响。
影响因子：
2.9
作者：
Sean T. Holmes;Olivia G Engl;Matthew N. Srnec;J. Madura;Rosalynn Quiñones;J. Harper;R. Schurko;R. Iuliucci
通讯作者：
R. Iuliucci
DOI：
10.1109/wsc.2002.1172944
发表时间：
2002-12
期刊：
Proceedings of the Winter Simulation Conference
影响因子：
--
作者：
O. Balci;R. Nance;James D. Arthur;William F. Ormsby
通讯作者：
O. Balci;R. Nance;James D. Arthur;William F. Ormsby
一些氨基酸的固态 14N 魔角旋转 NMR 研究。
影响因子：
2.2
作者：
T. Giavani;H. Bildsøe;J. Skibsted;H. J. Jakobsen
通讯作者：
H. J. Jakobsen