Attosecond delay in the molecular photoionization of asymmetric molecules.

We report theoretical calculations of the delay in photoemission from CO with particular emphasis on the role of the ultrafast electronic bound dynamics. We study the delays in photoionization in the HOMO and HOMO-1 orbitals of the CO molecule by looking into the stereo Wigner time delay technique. That compares the delay in photoemission from electrons emitted to the left and right to extract structural and dynamical information of the ionization process. For this we apply two techniques: The attosecond streak camera and the time of flight technique. Although they should provide the same results we have found large discrepancies of up to 36 in the case of HOMO, while for the HOMO-1 we obtain the same results with the two techniques. We have found that the large time delays observed in the HOMO orbital with the streaking technique are a consequence of the resonant transition triggered by the streaking field. This resonant transition produces a bound electron wavepacket that modifies the measurements of delay in photoionization. As a result of this observation, our technique allows us to reconstruct the bound wavepacket dynamics induced by the streaking field. By measuring the expected value of the electron momentum along the polarization direction after the streaking field has finished, we can recover the relative phase between the complex amplitudes of the HOMO and LUMO orbitals. These theoretical calculations pave the way for the measurement of ultrafast bound-bound electron transitionsand its crucial role for the delay in photoemission observation.