Kang Do Hyung, Kim Jinwoo, Noh Heung-Ryoul, Kim Sang Kyu
Department of Chemistry, KAIST, Daejeon, 34141, Republic of Korea.
Department of Physics, Chonnam National University, Gwangju, 61186, Republic of Korea.
Nat Commun. 2021 Dec 7;12(1):7098. doi: 10.1038/s41467-021-27468-1.
The ponderomotive force on molecular systems has rarely been observed hitherto, despite potentially being extremely useful for the manipulation of the molecular properties. Here, the ponderomotive effect in the non-valence bound states has been experimentally demonstrated, for the first time to the best of our knowledge, giving great promise for the manipulation of polyatomic molecules by the dynamic Stark effect. Entire quantum levels of the dipole-bound state (DBS) and quadrupole-bound state (QBS) of the phenoxide (or 4-bromophenoxide) and 4-cyanophenoxide anions, respectively, show clear-cut ponderomotive blue-shifts in the presence of the spatiotemporally overlapped non-resonant picosecond control laser pulse. The quasi-free electron in the QBS is found to be more vulnerable to the external oscillating electromagnetic field compared to that in the DBS, suggesting that the non-valence orbital of the former is more diffusive and thus more polarizable compared to that of the latter.
尽管质动力对分子系统可能极其有助于操控分子性质，但迄今为止很少被观测到。在此，据我们所知，首次通过实验证明了非价束缚态中的质动力效应，这为利用动态斯塔克效应操控多原子分子带来了巨大希望。分别在存在时空重叠的非共振皮秒控制激光脉冲时，苯氧负离子（或4 - 溴苯氧负离子）和4 - 氰基苯氧负离子的偶极束缚态（DBS）和四极束缚态（QBS）的整个量子能级都呈现出明显的质动力蓝移。与DBS中的准自由电子相比，发现QBS中的准自由电子更容易受到外部振荡电磁场的影响，这表明前者的非价轨道比后者更弥散，因此更具极化性。
