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We demonstrate picosecond, high-contrast population flipping of two-level atoms interacting with femtojoule optical pulses in a 3D photonic band gap waveguide. This is the result of giant Mollow splitting caused by strong light localization and a remarkable field-dependent relaxation of the atomic Bloch vector as it evolves near an abrupt jump in the electromagnetic density of states. Unlike steady-state switching, population inversion can remain nearly complete after the pulse subsides. Thisdoi:10.1103/physrevlett.103.233601 pmid:20366148 fatcat:swszqky7gjg3dgvjjbkc3tzx6i