Observation of the ponderomotive effect in non-valence bound states of polyatomic molecular anions.

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.