The relaxation of electronically excited atomic manganese isolated in solid rare gas matrices is observed from recorded emission spectra, to be strongly site specific. z P-6 state excitation of Mn atoms isolated in the red absorption site in Ar and Kr produces narrow a D-4 and a D-6 state emissions while blue-site excitation produces z P-6 state fluorescence and broadened a D-4 and a D-6 emissions. Mn/Xe exhibits only a single thermally stable site whose emission at 620 nm is similar to the broad a D-6 bands produced with blue-site excitation in Ar and Kr. Thus in Ar(Kr), excitation of the red site at 393 (400) nm produces narrow line emissions at 427.5 (427.8) and 590 (585.7) nm. From their spectral positions, linewidths, and long decay times, these emission bands are assigned to the a D-4(7/2) and a D-6(9/2) states, respectively. Excitation of the blue site at 380 (385.5) nm produces broad emission at 413 (416) nm which, because of its nanosecond radiative lifetime, is assigned to resonance z P-6 -> a S-6 fluorescence. Emission bands at 438 (440) and 625 (626.8) nm, also produced with blue-site excitation, are broader than their red-site equivalents at 427.5 and 590 nm (427.8 and 585.7 nm in Kr) but from their millisecond and microsecond decay times are assigned to the a D-4 and a D-6 states. The line features observed in high resolution scans of the red-site emission at 427.5 and 427.8 nm in Mn/Ar and Mn/Kr, respectively, have been analyzed with the W-p optical line shape function and identified as resolved phonon structure originating from very weak (S=0.4) electron-phonon coupling. The presence of considerable hot-phonon emission (even in 12 K spectra) and the existence of crystal field splittings of 35 and 45 cm(-1) on the excited a D-4(7/2) level in Ar and Kr matrices have been identified in W-p line shape fits. The measured matrix lifetimes for the narrow red-site a D-6 state emissions (0.29 and 0.65 ms) in Ar and Kr are much shorter than the calculated (3 s) gas phase value. With the lifetime of the metastable a D-6(9/2) state shortened by four orders of magnitude in the solid rare gases, it is clear that the probability of the "forbidden" a D-6 -> a S-6 atomic transition is greatly enhanced in the solid state. A novel feature identified in the present work is the large width and shifted D-4 and D-6 emissions produced for Mn atoms isolated in the blue sites of Ar and Kr. In contrast, these states produce narrow, unshifted (gas-phase-like) D-4 and D-6 state emissions from the red site. (c) 2005 American Institute of Physics.