High harmonic spectra show that laser-induced strong field ionization of water has a significant contribution from an inner-valence orbital. Our experiment uses the ratio of H2O and D2O high harmonic yields to isolate the characteristic nuclear motio
n of the molecular ionic states. The nuclear motion initiated via ionization of the highest occupied molecular orbital (HOMO) is small and is expected to lead to similar harmonic yields for the two isotopes. In contrast, ionization of the second least bound orbital (HOMO-1) exhibits itself via a strong bending motion which creates a significant isotope effect. We elaborate on this interpretation by simulating strong field ionization and high harmonic generation from the water isotopes using the time-dependent Schrodinger equation. We expect that this isotope marking scheme for probing excited ionic states in strong field processes can be generalized to other molecules.
The ionization probability of N$_2$, O$_2$, and CO$_2$ in intense laser fields is studied theoretically as a function of the alignment angle by solving the time-dependent Schrodinger equation numerically assuming only the single-active-electron appro
ximation. The results are compared to recent experimental data [D.~Pavi{v{c}}i{c} et al., Phys.,Rev.,Lett. {bf 98}, 243001 (2007)] and good agreement is found for N$_2$ and O$_2$. For CO$_2$ a possible explanation is provided for the failure of simplified single-active-electron models to reproduce the experimentally observed narrow ionization distribution. It is based on a field-induced coherent core-trapping effect.
