Spectroscopy of pendular molecules in strong parallel electric and magnetic fields
Spectroscopy of pendular molecules in strong parallel electric and magnetic fields
复制标题
强平行电场和磁场中摆动分子的光谱
DOI：
--
复制
发表时间：
1994
期刊：
影响因子：
--
通讯作者：
D. Herschbach
中科院分区：
文献类型：
--
作者：
B. Friedrich;A. Slenczka;D. Herschbach
作者报告了高分辨率。强平行电作用下 ICI 的 A3P1, n' - 19 <- X1S0+, n = 0 系统的激光诱导荧光光谱。和磁场，独立扫描高达 50 k V cm-1 和 0.7 T。任一场都会引起 A3P1 电子态内旋转态的相干叠加或杂化，该电子态同时具有电子和电子态。和沿核间轴的磁偶极矩。只有电动。场在基态 X1S0+ 内引起这种杂化，因为它是极性的但反磁性的。与计算光谱的比较说明了几个显着特征。杂交产生定向摆动状态，其中分子。轴被限制为在围绕场方向的有限角度范围内振动。对于极性顺磁电子态，例如A态，平行电。磁场共同为一半的集合产生杂交，但它们对另一半产生抵消作用。对于后一个组件，电。磁效应可以调整以平衡，但伴随的场引起的超精细分裂仍然存在，尽管分子自由旋转。转变强度对组合场的依赖性提供了明确的检测手段。电的相对符号。上电子态和下电子态的偶极矩。 X 和 A 态的符号相同（Cl 比 I 更负）。
The authors report high-resoln. laser-induced fluorescence spectra of the A3P1, n' - 19 <- X1S0+, n = 0 system of ICI subjected to strong parallel elec. and magnetic fields, scanned independently up to 50 k V cm-1 and 0.7 T. Either field induces coherent superposition or hybridization of the rotational states within the A3P1 electronic state, which possesses both an elec. and a magnetic dipole moment along the internuclear axis. Only the elec. field induces such hybridization within the ground state X1S0+, since it is polar but diamagnetic. Comparisons with computed spectra illustrate several salient features. The hybridization creates directional pendular states in which the mol. axis is confined to librate over a limited angular range about the field direction. For a polar paramagnetic electronic state, such as the A state, parallel elec. and magnetic fields conjoin in producing hybridization for half of the ensemble but they counteract for the other half. For the latter component, the elec. and magnetic effects can be tuned to balance out, yet the concomitant field-induced hyperfine splitting remains, despite the resulting free rotation of the mol. The dependence of the transition intensities on the combined fields provides an unequivocal means to det. the relative sign of the elec. dipole moments in the upper and lower electronic states. The sign is the same for the X and A states (Cl more neg. than I).