Fifth-order three-dimensional electronic spectroscopy using a pump-probe configuration.

We present the theoretical details and experimental demonstration of fifth-order three-dimensional (3D) electronic spectroscopy using a pump-probe beam geometry. This is achieved using a pulse shaper and appropriate phase cycling schemes. We show how 8-step and 27-step phase cycling schemes can measure purely absorptive 3D spectra as well as 3D spectra for the individual fifth-order processes that contribute to the purely absorptive spectrum. 3D spectra as a function of two separate controllable waiting time periods can be obtained. The peak shapes and positions of the peaks in the experimental measurement correspond well to theory.