Laser-induced electron diffraction of the ultrafast umbrella motion in ammonia

Abstract

Visualizing molecular transformations in real-time requires a structural retrieval method with Ångström spatial and femtosecond temporal atomic resolution. Imaging of hydrogen-containing molecules additionally requires an imaging method sensitive to the atomic positions of hydrogen nuclei, with most methods possessing relatively low sensitivity to hydrogen scattering. Laser-induced electron diffraction (LIED) is a table-top technique that can image ultrafast structural changes of gas-phase polyatomic molecules with sub-Ångström and femtosecond spatiotemporal resolution together with relatively high sensitivity to hydrogen scattering. Here, we image the umbrella motion of an isolated ammonia molecule (NH3) following its strong-field ionization. Upon ionization of a neutral ammonia molecule, the ammonia cation (NH3+) undergoes an ultrafast geometrical transformation from a pyramidal (φ HNH = 107 °) to planar (φ HNH = 120 °) structure in approximately 8 femtoseconds. Using LIED, we retrieve a near-planar (φ HNH = 117 ± 5 °) field-dressed NH3+ molecular structure 7.8 - 9.8 femtoseconds after ionization. Our measured field-dressed NH3+ structure is in excellent agreement with our calculated equilibrium field-dressed structure using quantum chemical ab initio calculations.