In this paper we utilize the molecular dynamics spectral density method to explore the absorption line shapes of the S-1(0) --> P-3(1)(6s[3/2](1)) electronic excitation of Xe in XeArN (N = 12-206) over the temperature range T = 10-40 K, with the Xe atom being located in distinct substitutional sites of the heterocluster (at T less than or equal to 30 K), or in an interior position in nonrigid and in amorphous clusters. The Xe(S-1(0) --> P-3(1)) extravalence excitations provide a sensitive microscopic probe for the local microenvironment of the Xe atom in these elemental clusters. The electronic excitations of Xe were described by the modified tight binding scheme (Webber, S.; Jortner, J.; Rice, S. A. J. Chem. Phys. 1965, 42, 1907) with reliable Xe(P-3(1))-Ar(S-1(0)) excited-state exp-6 pair potentials (Messing, I.; Rat, B.; jortner, J. J. Chem. Phys. 1977, 66, 2239). The site-specific and cluster-size-dependent spectroscopic observables were characterized in terms of the blue spectral shift delta nu of the absorption band peak, the spectral line width (FWHM) Gamma of the band, the spectral line shape, and their temperature dependence.