Body-fixed relativistic molecular Hamiltonian and its application to nuclear spin-rotation tensor: linear molecules.
Body-fixed relativistic molecular Hamiltonian and its application to nuclear spin-rotation tensor: linear molecules.
复制标题
DOI：
10.1063/1.4813594
复制
发表时间：
2013-07
期刊：
影响因子：
--
通讯作者：
Yunlong Xiao;Wenjian Liu
中科院分区：
文献类型：
--
作者：
Yunlong Xiao;Wenjian Liu
相对论性分子哈密顿量在体固定参考系中的表达是高精度计算涉及核振动和/或转动的光谱参数的基础。这种完全相对论地描述电子、准相对论地描述原子核的哈密顿量是针对半刚性非线性分子而发展起来的[Y. Xiao和W. Liu，J.Chem.Phys.138，134104（2013）]。然而，由于线性分子的一些不寻常的功能所产生的冗余的旋转围绕分子轴的制定应有所修订。尽管如此，所得到的同构哈密顿量是相当类似的非线性分子。因此，线性分子的核自旋-转动张量的相对论表述与非线性分子的非常相似。实验NSR和NMR之间的相对论映射也是如此。
The relativistic molecular Hamiltonian written in the body-fixed frame of reference is the basis for high-precision calculations of spectroscopic parameters involving nuclear vibrations and/or rotations. Such a Hamiltonian that describes electrons fully relativistically and nuclei quasi-relativistically is just developed for semi-rigid nonlinear molecules [Y. Xiao and W. Liu, J. Chem. Phys. 138, 134104 (2013)]. Yet, the formulation should somewhat be revised for linear molecules thanks to some unusual features arising from the redundancy of the rotation around the molecular axis. Nonetheless, the resulting isomorphic Hamiltonian is rather similar to that for nonlinear molecules. Consequently, the relativistic formulation of nuclear spin-rotation (NSR) tensor for linear molecules is very much the same as that for nonlinear molecules. So is the relativistic mapping between experimental NSR and NMR.