Linear Response in the Strong Field Domain

We show that, while it is well-known that first-order perturbation theory leads to linear response (of, e. g., a material system to an external field), the reverse is not true: linear response does not necessarily imply the validity of first-order perturbation theory, nor does it follow from it that the external perturbation is weak. We do so by analyzing the intensity dependence in the photoexcitation followed by dissociation or isomerization of a bound molecular system by a shaped broadband laser pulse. We show that, in certain cases where strong field effects are definitely present, the observed photoexcitation yield as a function of intensity may exhibit linear dependence over a wide range of intensities. The behavior is shown to coexist with a rather extensive range of coherent control over the branching ratios, an effect that was shown in the past to be impossible in the single precursor state (e. g., in the first-order perturbation theory) domain. For example, we demonstrate computationally that when (flat continuum-mediated) Raman transitions are present, appropriate pulse shaping can lead to a linear yield with intensity over a wide range of intensities, while coherent control over the branching ratio is significant. Thus, it is not necessary to invoke external bath effects (as is currently being done) to explain present-day experiments where coherent control is observed in the linear response regime.