Institute for Modeling and Technological Innovation, IMIT (CONICET-UNNE) and Natural and Exact Science Faculty, Northeastern University of Argentina, Avenida Libertad 5400, W3404AAS Corrientes, Argentina.
J Chem Phys. 2013 Sep 7;139(9):094112. doi: 10.1063/1.4819958.
In this work, relativistic effects on the nuclear spin-rotation (SR) tensor originated in the electron-nucleus and electron-electron Breit interactions are analysed. To this end, four-component numerical calculations were carried out in model systems HX (X=H,F,Cl,Br,I). The electron-nucleus Breit interaction couples the electrons and nuclei dynamics giving rise to a purely relativistic contribution to the SR tensor. Its leading order in 1/c is of the same value as that of relativistic corrections on the usual second order expression of the SR tensor considered in previous work [I. A. Aucar, S. S. Gómez, J. I. Melo, C. G. Giribet, and M. C. Ruiz de Azúa, J. Chem. Phys. 138, 134107 (2013)], and therefore it is absolutely necessary to establish its relative importance. For the sake of completeness, the corresponding effect originating in the electron-electron Breit interaction is also considered. It is verified that in all cases these Breit interactions yield only very small corrections to the SR tensors of both the X and H nuclei in the present series of compounds. Results of the present work strongly suggest that in order to achieve experimental accuracy in the theoretical study of the SR tensor both electron-nucleus and electron-electron Breit effects can be safely neglected.
在这项工作中，分析了源于电子-核和电子-电子 Breit 相互作用的核自旋-旋转（SR）张量的相对论效应。为此，在 HX（X=H，F，Cl，Br，I）模型系统中进行了四分量数值计算。电子-核 Breit 相互作用耦合了电子和核子的动力学，导致 SR 张量的纯相对论贡献。它在 1/c 中的一阶与先前工作中考虑的 SR 张量的相对论修正的二阶表达式的相对论修正相同[I. A. Aucar，S. S. Gómez，J. I. Melo，C. G. Giribet 和 M. C. Ruiz de Azúa，J. Chem. Phys. 138，134107（2013）]，因此绝对有必要确定其相对重要性。为了完整起见，还考虑了源于电子-电子 Breit 相互作用的相应效应。验证了在所有情况下，这些 Breit 相互作用仅对本系列化合物中 X 和 H 核的 SR 张量产生很小的修正。本工作的结果强烈表明，为了在 SR 张量的理论研究中达到实验精度，可以安全地忽略电子-核和电子-电子 Breit 效应。
