Vibrational-coherence measurement of nonequilibrium quantum systems by four-wave mixing

We show theoretically that a quantum system in a nonequilibrium state interacting with a set of laser pulses in a four-wave-mixing setup leads to signal emission in directions opposite to the ones usually considered. When combined with a pump mechanism which sets a time origin for the nonequilibrium state creation, this particular optical response can be utilized to directly follow decoherence processes in real time. By varying the time delays within the probe sequence, signals in these unconventional directions can also be used to detect two-dimensional spectra determined by the dynamics of up to three-quantum coherences, revealing energetical anharmonicities and environmental influences. As a numerical example, these findings are demonstrated by considering a model of vibrational decoherence of carbon monoxide after photolysis from a hemeprotein.