Pavanello Michele, Bubin Sergiy, Molski Marcin, Adamowicz Ludwik
Department of Chemistry, University of Arizona, Tucson, 85721, USA.
J Chem Phys. 2005 Sep 8;123(10):104306. doi: 10.1063/1.2012332.
Very accurate calculations of the pure vibrational spectrum of the HeH(+) ion are reported. The method used does not assume the Born-Oppenheimer approximation, and the motion of both the electrons and the nuclei are treated on equal footing. In such an approach the vibrational motion cannot be decoupled from the motion of electrons, and thus the pure vibrational states are calculated as the states of the system with zero total angular momentum. The wave functions of the states are expanded in terms of explicitly correlated Gaussian basis functions multipled by even powers of the internuclear distance. The calculations yielded twelve bound states and corresponding eleven transition energies. Those are compared with the pure vibrational transition energies extracted from the experimental rovibrational spectrum.
报道了对HeH(+)离子纯振动光谱的非常精确的计算。所采用的方法不假定玻恩-奥本海默近似，并且电子和原子核的运动被同等对待。在这种方法中，振动运动不能与电子运动解耦，因此纯振动态被计算为总角动量为零的系统状态。这些状态的波函数用明确相关的高斯基函数展开，并乘以核间距的偶次幂。计算得到了12个束缚态和相应的11个跃迁能量。将这些结果与从实验转动振动态光谱中提取的纯振动跃迁能量进行了比较。
