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

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 (NH 3 ) following its strong-field ionization. Upon ionization of a neutral ammonia molecule, the ammonia cation (NH 3 + ) 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 NH 3 + molecular structure 7.8 − 9.8 femtoseconds after ionization. Our measured field-dressed NH 3 + structure is in excellent agreement with our calculated equilibrium field-dressed structure using quantum chemical ab initio calculations.