Physical Chemistry

Observation of the Ponderomotive Effect in Non-Valence Bound States of Polyatomic Molecular Anions

Authors

Abstract

The ponderomotive effect in the non-valence bound states has been experimentally demonstrated for the first time, giving the great promise for the manipulation of the polyatomic molecules by the dynamic Stark effect. Entire quantum levels of the dipole-bound state (DBS) and quadruple-bound state (QBS) of the phenoxide (or 4-bromophenoxide) and 4-cyanophenoxide anions, respectively, show the 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.

Content

Thumbnail image of NBSStark-2021-Sept-02-ChemRxiv.pdf

Supplementary material

Thumbnail image of SI-NBSStark-2021-Sept-02-ChemRxiv.pdf
Supplementary Materials for Observation of the Ponderomotive Effect in Non-Valence Bound States of Polyatomic Molecular Anions
supplementary Materials for the details of the pump/probe power dependent photodetachment spectrum, procedure for evaluating the ponderomotive shift from the 4-cyanophenoxide QBS and phenoxide/4-bromophenoxide DBS, and laser intensity calculation methods.