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.

中文翻译：

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使用簇和碎片校正平面波密度泛函理论预测结晶固体中的 35-Cl 电场梯度张量


平面波校正方法已被证明可以有效地精确模拟晶体系统中的核磁共振 (NMR) 参数。最近的工作将平面波校正计算的应用扩展到第二行之外，使用投影增强波 (PAW) 密度泛函理论 (DFT) 的简单分子校正来预测 Cl 的 EFG 张量参数。在这里，我们使用基于片段和簇的计算以及可极化连续谱 (PCM) 方法来扩展这项工作，以进一步提高平面波校正 Cl EFG 张量计算的准确性。由含氯分子晶体和结晶氯化物盐的 105 个单独的 Cl EFG 张量主成分组成的测试集的基准数据显示，使用 PBE0 混合密度泛函进行片段校正平面波计算，将预测 EFG 张量成分的准确性提高了 30%传统的平面波计算。我们比较了不同几何优化方法和密度泛函对预测 Cl EFG 张量参数准确性的影响。提出了四种光谱分配案例，以证明提高预测 Cl EFG 张量参数准确性的实用性。