Fully absorptive 3D IR spectroscopy using a dual mid-infrared pulse shaper.

This paper presents the implementation of 3D IR spectroscopy by adding a second pump beam to a two-beam 2D IR spectrometer. An independent mid-IR pulse shaper is used for each pump beam, which can be programmed to collect its corresponding dimension in either the frequency or time-domains. Due to the phase matching geometry employed here, absorptive 3D IR spectra are automatically obtained, since all four of the rephasing and non-rephasing signals necessary to generate absorptive spectra are collected simultaneously. Phase cycling is used to isolate the fifth-order from the third-order signals. The method is demonstrated on tungsten hexacarbonyl (W(CO)6) and dicarbonylacetylacetonato rhodium (I), for which the eigenstates are extracted up to the third excited state. Pulse shaping affords a high degree of control over 3D IR experiments by making possible mixed time- and frequency-domain experiments, fast data acquisition and straightforward implementation.