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We present a technique for standoff trace chemical sensing that is based on the dependence of excited electronic state lifetimes on the amount of internal vibrational energy. The feasibility of the technique is demonstrated using N,N-dimethylisopropylamine (DMIPA). Time-resolved measurements show that the lifetime of the S 1 state in DMIPA exponentially decreases with the amount of vibrational energy. This property is employed to acquire molecular spectral signatures. Two laser pulses are used:doi:10.1364/ol.38.004445 pmid:24177115 fatcat:izfytvq2lfcrhc3uvd2o5br3ua