Rusakova Irina L, Rusakov Yuriy Yu, Krivdin Leonid B
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences , Favorsky St. 1, 664033 Irkutsk, Russian Federation.
J Phys Chem A. 2017 Jun 29;121(25):4793-4803. doi: 10.1021/acs.jpca.7b03198. Epub 2017 Jun 14.
Four-component relativistic calculations of Te NMR chemical shifts were performed in the series of 13 organotellurium compounds, potential precursors of the biologically active species, at the density functional theory level under the nonrelativistic and four-component fully relativistic conditions using locally dense basis set scheme derived from relativistic Dyall's basis sets. The relativistic effects in tellurium chemical shifts were found to be of as much as 20-25% of the total calculated values. The vibrational and solvent corrections to Te NMR chemical shifts are about, accordingly, 6 and 8% of their total values. The PBE0 exchange-correlation functional turned out to give the best agreement of calculated tellurium shifts with their experimental values giving the mean absolute percentage error of 4% in the range of ∼1000 ppm, provided all corrections are taken into account.
在密度泛函理论水平下，使用从相对论性戴尔基组导出的局部密集基组方案，在非相对论和四分量完全相对论条件下，对13种有机碲化合物（生物活性物种的潜在前体）系列进行了碲核磁共振化学位移的四分量相对论计算。发现碲化学位移中的相对论效应高达总计算值的20 - 25%。相应地，碲核磁共振化学位移的振动和溶剂校正分别约为其总值的6%和8%。结果表明，如果考虑所有校正，PBE0交换相关泛函给出的计算碲位移与其实验值的一致性最佳，在约1000 ppm范围内平均绝对百分比误差为4%。
