Yurchenko Sergei N, Thiel Walter, Patchkovskii Serguei, Jensen Per
Max-Planck-Institut für Kohlenforschung, Kaiser- Wilhelm-Platz 1, D-45470 Mülheim an der Ruhr, Germany.
Phys Chem Chem Phys. 2005 Feb 21;7(4):573-82. doi: 10.1039/b418073a.
We investigate theoretically the rotational dynamics of pyramidal XY3 molecules in highly excited rotational states. Towards this end we compute, by a variational method, the rotational energy levels in the vibrational ground state of PH3 for J < or = 80. At J > or = 50 the calculated energy levels show a distinct cluster pattern. By monitoring the cluster formation we follow the various stages of the rotational dynamics. We analyze the wavefunctions for the cluster states and compute expectation values which show that the C3v geometrical symmetry of PH3 is broken at high rotational excitation. The conclusions drawn from the quantum-mechanical calculations are confirmed by semi-classical theory, i.e., by an analysis of the stationary points on the rotational energy surface.
我们从理论上研究了处于高激发转动态的三角锥形XY3分子的转动动力学。为此，我们通过变分法计算了J≤80时PH3振动基态的转动能级。在J≥50时，计算得到的能级呈现出明显的聚类模式。通过监测聚类形成过程，我们追踪转动动力学的各个阶段。我们分析了聚类态的波函数并计算了期望值，结果表明在高转动激发下PH3的C3v几何对称性被打破。量子力学计算得出的结论通过半经典理论得到了证实，即通过对转动能量表面上的驻点进行分析得到了证实。
