Relativistic nuclear magnetic resonance J-coupling with ultrasoft pseudopotentials and the zeroth-order regular approximation
Relativistic nuclear magnetic resonance J-coupling with ultrasoft pseudopotentials and the zeroth-order regular approximation
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DOI：
10.1063/1.4882678
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发表时间：
2014-06-21
影响因子：
4.4
通讯作者：
Yates, Jonathan R.
中科院分区：
文献类型：
--
作者：
Green, Timothy F. G.;Yates, Jonathan R.
我们提出了一种方法的第一性原理计算的核磁共振（NMR）J-耦合在扩展系统中使用最先进的超软赝势和包括标量相对论效应。通过扩展Joyce等人[J. Chem. Phys. 127，204 - 107（2007）]的投影增强波（PAW）方法，允许使用超软赝势。我们基准它对现有的本地轨道量子化学计算和实验的小分子含有轻元素，具有良好的协议。标量相对论效应包括在零阶正规近似水平的理论和基准对现有的本地轨道量子化学计算和实验的一些小分子含有重行六元素W，Pt，Hg，Tl，和Pb，具有良好的协议。最后，（1）J（P-Ag）和（2）J（P-Ag-P）耦合在一些较大的分子晶体中进行了计算，并与固态NMR实验进行了比较。对如何提高等离子体波偶极子微扰的数值稳定性也作了一些评论。(C)2014 AIP Publishing LLC.
We present a method for the first-principles calculation of nuclear magnetic resonance (NMR) J-coupling in extended systems using state-of-the-art ultrasoft pseudopotentials and including scalar-relativistic effects. The use of ultrasoft pseudopotentials is allowed by extending the projector augmented wave (PAW) method of Joyce et al. [J. Chem. Phys. 127, 204107 (2007)]. We benchmark it against existing local-orbital quantum chemical calculations and experiments for small molecules containing light elements, with good agreement. Scalar-relativistic effects are included at the zeroth-order regular approximation level of theory and benchmarked against existing local-orbital quantum chemical calculations and experiments for a number of small molecules containing the heavy row six elements W, Pt, Hg, Tl, and Pb, with good agreement. Finally, (1)J(P-Ag) and (2)J(P-Ag-P) couplings are calculated in some larger molecular crystals and compared against solid-state NMR experiments. Some remarks are also made as to improving the numerical stability of dipole perturbations using PAW. (C) 2014 AIP Publishing LLC.