NMR Research Group, Department of Physics, University of Oulu, P.O. Box 3000, FIN-90014 Oulu, Finland.
J Chem Phys. 2014 Jan 14;140(2):024103. doi: 10.1063/1.4855315.
Nuclear magneto-optic effects could make important contributions to novel, high-sensitivity, and high-resolution spectroscopic and imaging methods that provide nuclear site-specific structural and dynamic information on molecular and materials systems. Here we present a first-principles electronic structure formulation of nuclear quadrupole moment-induced Cotton-Mouton effect in terms of response theory, as well as ab initio and density-functional theory calculations of this phenomenon for a series of molecular liquids: H2O, CH3NO2, CH3CH2OH, C6H6, C6H12 (cyclohexane), HI, XeF2, WF5Cl, and Pt(C2dtp)2. The roles of basis-set convergence, electron correlation, and relativistic effects are discussed. The estimated order of magnitude of the overall ellipticities induced to linearly polarized light is 10(-3)-10(-7) rad/(M cm) for fully spin polarized nuclei. The cases with the largest presently obtained ellipticities should be detectable with modern instrumentation in the Voigt magneto-optic setup, particularly for the heavy nuclei.
核旋磁光效应对新型高灵敏度、高分辨率光谱学和成像方法可能会有重要贡献，这些方法可提供分子和材料系统中核特定位置的结构和动态信息。在这里，我们提出了一种基于响应理论的核四极矩诱导考顿-穆顿效应的第一性原理电子结构公式，并对一系列分子液体（H2O、CH3NO2、CH3CH2OH、C6H6、C6H12（环己烷）、HI、XeF2、WF5Cl 和 Pt(C2dtp)2）进行了该现象的从头算和密度泛函理论计算。讨论了基集收敛、电子相关和相对论效应对核四极矩诱导考顿-穆顿效应的影响。对于完全极化的核，线性偏振光诱导的整体椭圆率的估计量级为 10(-3)-10(-7) rad/(M cm)。在 Voigt 磁光设置中，使用现代仪器应该可以检测到目前获得的最大椭圆率的情况，尤其是对于重核。
