The focus of this article is on the different behavior of large deviations of random functionals associated with the parabolic Anderson model above the mean versus large deviations below the mean. The functionals we treat are the solution u(x, t) to the spatially discrete parabolic Anderson model and a functional A n which is used in analyzing the a.s. Lyapunov exponent for u(x, t). Both satisfy a “law of large numbers”, with $${\lim_{t\to \infty} \frac{1}{t} \log u(x,t)=\lambda (\kappa)}$$ and $${\lim_{n\to \infty} \frac{A_n}{n}=\alpha}$$ . We then think of αn and λ(κ)t as being the mean of the respective quantities A n and log u(t, x). Typically, the large deviations for such functionals exhibits a strong asymmetry; large deviations above the mean take on a different order of magnitude from large deviations below the mean. We develop robust techniques to quantify and explain the differences.

The role of the nuclear degrees of freedom in nonlinear two-photon single ionization of H_{2} molecules interacting with short and intense vacuum ultraviolet pulses is investigated, both experimentally and theoretically, by selecting single resonant vibronic intermediate neutral states. This high selectivity relies on the narrow bandwidth and tunability of the pulses generated at the FERMI free-electron laser. A sustained enhancement of dissociative ionization, which even exceeds nondissociative ionization, is observed and controlled as one selects progressively higher vibronic states. With the help of ab initio calculations for increasing pulse durations, the photoelectron and ion energy spectra obtained with velocity map imaging allow us to identify new photoionization pathways. With pulses of the order of 100 fs, the experiment probes a timescale that lies between that of ultrafast dynamical processes and that of steady state excitations.