Capistran Daniel, Harper James K, Hartman Joshua D
Department of Chemistry, University of CaliforniaRiverside, Riverside, CA, USA.
Chemistry and Biochemistry, Brigham Young University, Provo, UT, USA.
Solid State Nucl Magn Reson. 2024 Oct;133:101949. doi: 10.1016/j.ssnmr.2024.101949. Epub 2024 Aug 8.
Planewave-corrected methods have proven effective for accurately modeling nuclear magnetic resonance (NMR) parameters in crystalline systems. Recent work extended the application of planewave-corrected calculations beyond the second row, predicting EFG tensor parameters for Cl using a simple molecular correction to projector augmented-wave (PAW) density functional theory (DFT). Here we extend this work using fragment and cluster-based calculations coupled with polarizable continuum (PCM) methods to improve further the accuracy of planewave-corrected Cl EFG tensor calculations. Benchmark data from a test set comprised of 105 individual Cl EFG tensor principal components for chlorine-containing molecular crystals and crystalline chloride salts shows fragment-corrected planewave calculations using the PBE0 hybrid density functional improve the accuracy of predicted EFG tensor components by 30 % relative to traditional planewave calculations. We compare the influence of different geometry optimization methods and density functionals on the accuracy of predicted Cl EFG tensor parameters. Four cases of spectral assignment are presented to demonstrate the utility of improving the accuracy of predicted Cl EFG tensor parameters.
平面波校正方法已被证明在精确模拟晶体系统中的核磁共振（NMR）参数方面是有效的。最近的工作将平面波校正计算的应用扩展到了第二周期以外，通过对投影增强波（PAW）密度泛函理论（DFT）进行简单的分子校正来预测Cl的电场梯度（EFG）张量参数。在此，我们通过基于片段和团簇的计算以及极化连续介质（PCM）方法来扩展这项工作，以进一步提高平面波校正的Cl EFG张量计算的准确性。由105个含氯分子晶体和结晶氯化物盐的单个Cl EFG张量主成分组成的测试集的基准数据表明，使用PBE0杂化密度泛函的片段校正平面波计算相对于传统平面波计算，将预测的EFG张量成分的准确性提高了30%。我们比较了不同几何优化方法和密度泛函对预测的Cl EFG张量参数准确性的影响。给出了四个光谱归属的案例，以证明提高预测的Cl EFG张量参数准确性的实用性。
