Relaxation of photoexcited Na _3 F

. This paper describes the spectroscopy of Na 3 F both in the frequency and time domains. The photoionization efficiency curve shows two thresholds, associated to two isomers. The excited electronic states of the C 2 v isomer have been probed by photodepletion spectroscopy, and the results are used to analyze a time-resolved study of photoexcited Na 3 F, probed by photoionization. The pump-probe signal clearly shows damped oscillations, the period of which is fitted to 390±10 fs, close to twice the previously measured bending mode of Na 2 F [1], while the relaxation time is 1275±50 fs.