Attosecond Nuclear Dynamics in the Ammonia Cation: Relation between High-Harmonic and Photoelectron Spectroscopies

We report measurements of the umbrella motion in the ammonia cation on the attosecond time scale. The motion is prepared by strong‐field ionization and probed by photorecombination through the process of high‐harmonic generation. Performing such measurements at multiple wavelengths (0.8, 1.44, 1.8 μm) enables us to follow the nuclear dynamics over a broad temporal range (0.8–3.8 fs). The intensity of the driving field is found to have a significant impact on the observed dynamics through the vibrational‐state dependence of the strong‐field ionization rates. We derive a general model that includes these effects and establishes a new link between high‐harmonic spectroscopy and classical photoelectron spectroscopy. Our model reproduces the observed dynamics and their dependence on the intensity of the driving field. Moreover, the model predicts much richer nuclear dynamics on the few‐fs timescale than most previous theories. The newly predicted features are shown to reflect the quantized vibronic level structure of the molecular cation. Measurements of the umbrella motion in the ammonia cation on the subfemtosecond time scale are reported (see picture). The motion is prepared by strong‐field ionization and probed by photorecombination through the process of high‐harmonic generation. A general model that establishes a new link between high‐harmonic spectroscopy and classical photoelectron spectroscopy is presented.