Electronic quantum effects mapped onto non-Born-Oppenheimer nuclear paths: nonclassical surmounting over potential barriers and trapping above the transition states due to nonadiabatic path-branching.

摘要: We develop the path-branching representation for nonadiabatic electron wavepacket dynamics [T. Yonehara and K. Takatsuka, J. Chem. Phys. 132, 244102 (2010)] so as to treat in an energy range comparable barrier height of adiabatic potential curves. With this two characteristic chemical reaction are studied, which incident nuclear encounters a barrier, on top lies another nonadiabatically coupled curve: (1) Dynamics initial paths coming into interaction region with lower than height. They branch pieces (and repeat branching subsequently), upper counterparts can penetrate classically inaccessible high eventually back product ground state curve. This is say surmounting via excited state, phenomenologically looks like so-called deep tunneling. (2) classical whose energies little higher but may be bottom state. undergo some those components trapped being followed by population decay down flowing both reactant sites. Such expectations arising from numerically confirmed full quantum mechanical dynamics. phenomenon experimentally observed time-delayed pulses trains.