In apparatus and methods of Raman spectroscopy in air, a target region is excited by a laser pump pulse exceeding the critical power for self-focusing in air and having a duration after self-focusing of 15 fs or less. A laser probe pulse having a duration in the range of 200 fs to 100 ps and an energy of at least 20 μJ is directed at the excited target region. Stimulated Raman scattering from the interaction between the excited target region and the laser probe pulse is detected. The target region can be outside the spectrometer, with ambient air in between used for the self-focusing.