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Do Double-Hybrid Exchange–Correlation Functionals Provide Accurate Chemical Shifts? A Benchmark Assessment for Proton NMR
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2021-10-12 , DOI: 10.1021/acs.jctc.1c00604
Marcelo T de Oliveira 1, 2 , Júlia M A Alves 2 , Ataualpa A C Braga 3 , David J D Wilson 1 , Cristina A Barboza 4
Affiliation  

A benchmark density functional theory (DFT) study of 1H NMR chemical shifts for data sets comprising 200 chemical shifts, including complex natural products, has been carried out to assess the performance of DFT methods. Two new benchmark data sets, NMRH33 and NMRH148, have been established. The meta-GGA revTPSS performs remarkably well against the NMRH33 benchmark set (mean absolute deviation (MAD), 0.10 ppm; maximum deviation (max), 0.26 ppm) with the smallest MAD of all evaluated functionals. The best-performing double-hybrid density functional (DHDF), revDSD-BLYP (MAD, 0.16 ppm; max, 0.35 ppm), performs similarly to hybrid-GGA methods (e.g., mPW1PW91/6-311G(d) (MAD, 0.15 ppm; max, 0.36 ppm)), but at a considerably higher computational cost. The results indicate that currently available double-hybrid DFT methods offer no benefit over GGA (including hybrid and meta) functionals in the calculation of 1H NMR chemical shifts.

中文翻译:

双杂化交换-相关泛函是否提供准确的化学位移?质子核磁共振的基准评估

基准密度泛函理论 (DFT) 研究1已对包含 200 个化学位移(包括复杂的天然产物)的数据集进行 H NMR 化学位移,以评估 DFT 方法的性能。已建立两个新的基准数据集 NMRH33 和 NMRH148。meta-GGA revTPSS 与 NMRH33 基准集(平均绝对偏差 (MAD),0.10 ppm;最大偏差 (max),0.26 ppm)相比表现非常好,所有评估的函数的 MAD 最小。性能最佳的双混合密度泛函 (DHDF),revDSD-BLYP(MAD,0.16 ppm;最大值,0.35 ppm),其性能类似于混合 GGA 方法(例如,mPW1PW91/6-311G(d)(MAD,0.15 ppm;最大值,0.36 ppm)),但计算成本要高得多。1 H NMR化学位移。
更新日期:2021-11-09
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