Monitoring the effect of a control pulse on a conical intersection by time-resolved photoelectron spectroscopy.

We have previously shown how femtosecond angle- and energy-resolved photoelectron spectroscopy can be used to monitor quantum wavepacket bifurcation at an avoided crossing or conical intersection and also how a symmetry-allowed conical intersection can be effectively morphed into an avoided crossing by photo-induced symmetry breaking. The latter result suggests that varying the parameters of a laser to modify a conical intersection might control the rate of passage of wavepackets through such regions, providing a gating process for different chemical products. In this paper, we show with full quantum mechanical calculations that such optical control of conical intersections can actually be monitored in real time with femtosecond angle- and energy-resolved photoelectron spectroscopy. In turn, this suggests that one can optimally control the gating process at a conical intersection by monitoring the photoelectron velocity map images, which should provide far more efficient and rapid optimal control than measuring the ratio of products. To demonstrate the sensitivity of time-resolved photoelectron spectra for detecting the consequences of such optical control, as well as for monitoring how the wavepacket bifurcation is affected by the control, we report results for quantum wavepackets going through the region of the symmetry-allowed conical intersection between the first two (2)A' states of NO(2) that is transformed to an avoided crossing. Geometry- and energy-dependent photoionization matrix elements are explicitly incorporated in these studies. Time-resolved photoelectron angular distributions and photoelectron images are seen to systematically reflect the effects of the control pulse.