Center for Free-Electron Laser Science, DESY, Notkestrasse 85, 22607 Hamburg, Germany.
Department of Physics, University of Hamburg, Jungiusstrasse 9, 20355 Hamburg, Germany.
Phys Rev Lett. 2018 Mar 23;120(12):123001. doi: 10.1103/PhysRevLett.120.123001.
The effect of nuclear dynamics and conical intersections on electronic coherences is investigated employing a two-state, two-mode linear vibronic coupling model. Exact quantum dynamical calculations are performed using the multiconfiguration time-dependent Hartree method. It is found that the presence of a nonadiabatic coupling close to the Franck-Condon point can preserve electronic coherence to some extent. Additionally, the possibility of steering the nuclear wave packets by imprinting a relative phase between the electronic states during the photoionization process is discussed. It is found that the steering of nuclear wave packets is possible given that a coherent electronic wave packet embodying the phase difference passes through a conical intersection. A conical intersection close to the Franck-Condon point is thus a necessary prerequisite for control, providing a clear path towards attochemistry.
采用两态两模线性振子耦合模型研究了核动力学和锥形交叉对电子相干性的影响。利用多组态含时哈特ree 方法进行了精确的量子动力学计算。结果表明，在 Franck-Condon 点附近存在非绝热耦合可以在一定程度上保持电子相干性。此外，还讨论了在光致电离过程中通过在电子态之间引入相对相位来控制核波包的可能性。结果表明，只有当包含相位差的相干电子波包穿过锥形交叉时，才有可能控制核波包。因此，Franck-Condon 点附近的锥形交叉是控制的必要前提，为原子分子化学开辟了明确的途径。
