Instantaneous nonvertical electronic transitions with shaped femtosecond laser pulses: Is it possible?

In molecular electronic transitions, a vertical transition can be induced by an ultrashort laser pulse. That is, a replica of the initial nuclear state-times the transition dipole moment of the electronic transition-can be created instantaneously (on the time scale of nuclear motion) in the excited electronic state.

Now, applying pulse shaping via the modulation of the phases of each spectral component of an ultrashort pulse, it is tempting to ask whether it is also possible to induce instantaneous nonvertical transitions to bound electronic states, provided that the phases of each spectral component of the pulse are set to appropriate values at the discrete frequencies corresponding to the energy levels of the potential.

We analyze the problem in the weak-field limit, and show that such a phase requirement cannot be encoded into an ultrashort pulse. This result is equivalent to the statement that it is not possible to move matter faster than the time associated with the natural (field-free) dynamics of the system.