由非绝热相关获得的形式量子数及其在高激发振动态的经典解释

我们利用非绝热相关方法 ,通过关闭所有的振动模式间的耦合项并追溯到零级本征态 ,以得到体系的形式量子数 ,将形式量子数对高激发振动态的能级谱图进行归属 ,并重构本征能级图谱 ,使本征能级以有序的方式排列。这有助于对高激发振动态的能级进行分类和归属。形式量子数是体现高激发振动态的重要特征 ,是高激发振动态的近似运动守恒量。我们将多维陪集相空间的经典方法应用于高激发态的研究 ,发现形式量子数对应的李雅普诺夫指数为零或最小 ,并且它对应于较大的相空间密度

Formal Quantum Numbers As Retrieved By the Diabatic Correlation and Their Classical Interpretation For the Highly Excited Vibrational Eigenstates

Formal quantum numbers as retrieved via diabatic correlation to the zero-order states where all inter-mode couplings are switched off can be assigned to the eigenstates for the molecular highly excited vibration. These formal quantum numbers can be employed to reconstruct the eigenstates in a regular way. This helps the classification and assignment of the highly excited vibrational states. Formal quantum numbers are shown as approximate constants of motion. Classical approach in a multi-dimensional coset phase space to the highly excited vibration is employed to show that formal quantum numbers are with zero or least Lyapunov exponents and correspond to significant phase space density.