We report the first observation of a non-dipole transition in an ultra-cold atomic vapor. We excite the 3P-4P electric quadrupole (E2) transition in $^{23}$Na confined in a Magneto-Optical Trap(MOT), and demonstrate its application to high-resolution spectroscopy by making the first measurement of the hyperfine structure of the 4P$_{1/2}$ level and extracting the magnetic dipole constant A $=$ 30.6 $pm$ 0.1 MHz. We use cw OODR (Optical-Optical Double Resonance) accompanied by photoinization to probe the transition.
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