Coherent control of multiple vibrational excitations for optimal detection

While the means to selectively excite a single vibrational mode using ultrafast pulse shaping are well established, the subsequent problem of selectively exciting multiple vibrational modes simultaneously has been largely neglected. The coherent control of multiple vibrational excitations has applications in control of chemistry, chemical detection and molecular vibrational quantum information processing. Using simulations and experiments, we demonstrate that multiple vibrational modes can be selectively excited with the concurrent suppression of multiple interfering modes by orders of magnitude. While the mechanism of selectivity is analogous to that of single mode selectivity, the interferences required to select multiple modes require complicated non-intuitive pulse trains. Additionally, we show that selective detection can be achieved by the optimal pulse shape, even when the nature of the interfering species is varied, suggesting that optimized detection should be practical in real world applications. Experimental measurements of the multiplex coherent anti-Stokes Raman spectra (CARS) and CARS decay times of toluene, acetone, cis-stilbene and nitromethane liquids are reported, along with optimizations attempting to selectively excite nitromethane in a mixture of the four solvents. The experimental implementation exhibits a smaller degree of signal to background enhancement than predicted, which is primarily attributed to the single objective optimization methodology and not to fundamental limitations.