Rusakov Yuriy Yu, Nikurashina Yuliya A, Rusakova Irina L
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, 664033 Irkutsk, Russian Federation.
Phys Chem Chem Phys. 2025 Mar 26;27(13):6730-6743. doi: 10.1039/d5cp00313j.
In this paper, we demonstrate that the accuracy of calculated solvent corrections to P NMR shielding constants of various phosphorus-containing molecules significantly depends on the basis set used. The highly positive role played by diffuse functions was revealed not only for the solvent corrections but also for phosphorus NMR shielding constants of anions. Considering this matter, the augmentation in shift-oriented pecS- ( = 1 and 2) basis sets for phosphorus atoms with diffuse functions was carried out using the property-energy consistent (PEC) method with isotropic dipole polarizability used as the main target property, which is the first example of such augmentation of basis sets. Alongside other augmented basis sets of different types and qualities, the new aug-pecS- ( = 1 and 2) basis sets were shown to significantly improve the accuracy of solvent corrections to the P NMR shielding constants of neutral molecules and phosphorus shielding constants of anions compared with their non-augmented analogs. Finally, comparison with available experimental data corroborated our theoretical findings.
在本文中，我们证明了对各种含磷分子的³¹P NMR屏蔽常数计算的溶剂校正精度显著取决于所使用的基组。不仅对于溶剂校正，而且对于阴离子的³¹P NMR屏蔽常数，弥散函数都发挥了高度积极的作用。考虑到这一点，使用以各向同性偶极极化率为主要目标性质的性质 - 能量一致（PEC）方法，对具有弥散函数的磷原子的位移导向pecS-（l = 1和2）基组进行了扩充，这是此类基组扩充的首个实例。与其他不同类型和质量的扩充基组一起，新的aug-pecS-（l = 1和2）基组与未扩充的类似基组相比，显著提高了中性分子³¹P NMR屏蔽常数的溶剂校正精度以及阴离子的磷屏蔽常数精度。最后，与现有实验数据的比较证实了我们的理论发现。
