Nuclear quantum dynamics on the ground electronic state of neutral silver dimer AgAg probed by femtosecond NeNePo spectroscopy.

The nuclear quantum dynamics on the ground electronic state of the neutral silver dimer AgAg are studied by femtosecond (fs) pump-probe spectroscopy using the 'negative ion - to neutral - to positive ion' (NeNePo) excitation scheme. A vibrational wave packet is prepared on the XΣ+g state of Ag photodetachment of mass-selected, cryogenically cooled Ag using a first ultrafast pump laser pulse. The temporal evolution of the wave packet is then probed by an ultrafast probe pulse resonant multiphoton ionization to Ag. Frequency analysis of the fs-NeNePo spectra obtained for a single isotopologue and pump-probe delay times up to 60 ps yields the harmonic ( = 192.2 cm), quadratic anharmonic ( = 0.637 cm) and cubic anharmonic ( = 3 × 10 cm) constants for the XΣ+g state of neutral Ag. The fs-NeNePo spectra obtained at different pump wavelengths provide insight into the excitation mechanism. At a pump wavelength of 510 nm instead of 1010 nm, resonant excitation of a short-lived electronically excited state of the anion followed by autodetachment results in population of higher-energy vibrational levels of the neutral ground state. In contrast, at 1140 nm dynamics with a slightly shorter beating period and different relative phase are observed. The present study demonstrates that isotopologue-specific fs-NeNePo spectroscopy provides accurate vibrational constants of mass-selected neutral clusters in their electronic ground state in the terahertz spectral region, which remains difficult to obtain directly in the frequency domain with any other type of spectroscopy of comparable sensitivity.