Takatsuka Kazuo, Arasaki Yasuki
Fukui Institute for Fundamental Chemistry, Kyoto University, 606-8103 Kyoto, Japan.
J Chem Phys. 2024 Aug 14;161(6). doi: 10.1063/5.0219345.
The quantum nuclear kinematic interactions with electrons (or nonadiabatic interactions) are the inherent driving force that possibly causes a mixture of the adiabatic electronic states in molecules. Particularly in systems whose electron wavepackets lie in a densely quasi-degenerate electronic-state manifold where many-dimensional and many-state nonadiabatic interactions last continually, we have found before that those extensive mixings can lead to a quantum electronic-state chaos [K. Takatsuka and Y. Arasaki, J. Chem. Phys. 159, 074110 (2023)]. This chaos of electron dynamics is a new kind yet generic. This Communication identifies the mathematical/physical mechanism of this class of chaos by means of the collective coordinate analysis of the nonadiabatic interactions, along with the numerical applications to excited states of boron clusters. Some physical consequences of the present chaos are also discussed.
量子核与电子的运动学相互作用（或非绝热相互作用）是可能导致分子中绝热电子态混合的内在驱动力。特别是在电子波包处于密集准简并电子态流形的系统中，其中多维和多态非绝热相互作用持续不断，我们之前已经发现，那些广泛的混合会导致量子电子态混沌 [K. 高冢和 Y. 荒崎，《化学物理杂志》159, 074110 (2023)]。这种电子动力学的混沌是一种新型的但具有普遍性的混沌。本通讯通过对非绝热相互作用的集体坐标分析，以及对硼团簇激发态的数值应用，确定了这类混沌的数学/物理机制。还讨论了当前混沌的一些物理后果。
