Intermolecular vibrations and spin–orbit predissociation dynamics of NeOH (X 2Π)
Intermolecular vibrations and spin–orbit predissociation dynamics of NeOH (X 2Π)
复制标题
NeOH (X 2Π) 的分子间振动和自旋轨道预解离动力学
DOI：
10.1063/1.470226
复制
发表时间：
1995
影响因子：
4.4
通讯作者：
M. Lester
中科院分区：
文献类型：
--
作者：
C. Chuang;P. M. Andrews;M. Lester
NeOH的受激发射泵浦被用于获得OH X 2Π3/2+Ne势能面支持的结合分子间振动能级，以及与OH X 2Π1/2+Ne的自旋轨道激发态相关的预解离能级，这些能级高于解离极限100 cm−1以上。分子间拉伸间隔和转子常数产生了Ne和OH X之间平均相互作用的径向依赖性2Π3/2,1/2，而角能级之间的间距提供了势的各向异性信息。在分子间拉伸激发下，自旋轨道预解离能级的寿命增加了3倍，从8.5 ps增加到27 ps以上。这种寿命的增加是由于两个自旋轨道态之间的耦合随着分子间分离距离的增加而下降。自旋-轨道预解的主要耦合是由差势提供的，差势是分子间势的变化。
Stimulated emission pumping of NeOH is used to access the bound intermolecular vibrational levels supported by the OH X 2Π3/2+Ne potential energy surface as well as predissociative levels correlating with the spin–orbit excited state of OH X 2Π1/2+Ne which lie more than 100 cm−1 above the dissociation limit. Intermolecular stretching intervals and rotor constants yield the radial dependence of the average interaction between Ne and OH X 2Π3/2,1/2, while the spacings between angular levels provide information on the anisotropy of the potentials. The lifetime of spin–orbit predissociative levels is found to increase by a factor of 3 upon intermolecular stretching excitation, from 8.5 ps to more than 27 ps. This increase in lifetime is attributed to the fall‐off in the coupling between the two spin–orbit states with increasing intermolecular separation distance. The dominant coupling for spin–orbit predissociation is provided by the difference potential, the change in the intermolecular potential when the un...