Nuclear quadrupole moment-induced Cotton-Mouton effect in molecules

作者：Fu Li juan^*; Vaara Juha

来源：Journal of Chemical Physics, 2014, 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(C(2)dtp)(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.

• 出版日期2014-1-14