Hovering States of Ammonia in a High-Intensity, High-Frequency Oscillating Field: Trapped into Planarity by Laser-Induced Hybridization.

Abstract

A high-intensity, high-frequency laser can create an oscillating induced dipole moment in a molecule. At high laser frequencies with a long pulse width, a stable non-ionizing state with a laser-induced hybridization of the electrons is formed. For ammonia, aligned with the linear polarization direction of the laser, such stable states can be realized. Electronic hybridization in the presence of the high-frequency field is such that the lone pair propensity is dynamically equalized on either side of ammonia. This leads to a destabilization of pyramidal ammonia and hovering states with the electron density flipping to either side of the geometry. Electronic structure calculations in an oscillating frame of reference anticipate this effect with a predicted classical quiver distance of 0.1 Å. Electronic dynamics at a laser intensity of 1.14 × 1013 W/cm2 and a frequency of 8.16 eV predicts negligible ionization for the planar geometry. Approximate nuclear wave packet dynamics in the oscillating potential energy generated by the electrons predicts a trapping of ammonia in its planar transition state geometry.