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<p>The comparative analysis of the calculated and experimental <sup>195</sup>Pt NMR chemical shifts for a wide range of model platinum complexes shows that the density functional theory well reproduces the experimental data. The <sup>195</sup>Pt NMR chemical shifts can be calculated with high accuracy within the fully relativisitic four-component matrix Dirac—Kohn—Sham formalism (4c-mDKS) (<i>R</i><sup>2</sup> = 0.998, <i>RMSE</i> = 52 ppm, and <i>MDR</i> = 0.9%). The PBE0/{6–31+G(d); Pt(SDD)} approximation may be sufficient for geometry optimization of the complexes. However, the presence of heavy atoms directly bound to platinum requires consideration of their scalar relativistic effects on the geometry at the optimization stage. The problems of shielding calculation for the common [PtCl<sub>6</sub>]<sup>2−</sup> reference can be minimized performing an empirical linear correction. At the same time, if the pseudorelativistic approximation based on application of all-electron relativistically contracted basis sets (NMR-DKH) is used, the accuracy of estimation is several-fold worse (<i>R</i><sup>2</sup> = 0.968, <i>RMSE</i> = 200 ppm, and <i>MDR</i> = 2.9%), even with linear correction for reducing large systematic errors.</p>

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Reliable DFT protocol for calculation of 195Pt NMR chemical shifts

  • 期刊论文

  • 发表日期：

    2025年10月1日

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  • S. A. Kondrashova,
  • Sh. K. Latypov

摘要

The comparative analysis of the calculated and experimental 195Pt NMR chemical shifts for a wide range of model platinum complexes shows that the density functional theory well reproduces the experimental data. The 195Pt NMR chemical shifts can be calculated with high accuracy within the fully relativisitic four-component matrix Dirac—Kohn—Sham formalism (4c-mDKS) (R2 = 0.998, RMSE = 52 ppm, and MDR = 0.9%). The PBE0/{6–31+G(d); Pt(SDD)} approximation may be sufficient for geometry optimization of the complexes. However, the presence of heavy atoms directly bound to platinum requires consideration of their scalar relativistic effects on the geometry at the optimization stage. The problems of shielding calculation for the common [PtCl6]2− reference can be minimized performing an empirical linear correction. At the same time, if the pseudorelativistic approximation based on application of all-electron relativistically contracted basis sets (NMR-DKH) is used, the accuracy of estimation is several-fold worse (R2 = 0.968, RMSE = 200 ppm, and MDR = 2.9%), even with linear correction for reducing large systematic errors.