Low temperature photoluminescence results from high purity epitaxial GaAs are presented, and a new type of transition involving negatively charged donor ions and neutral acceptors is identified. At low temperatures and excitation densities this becomes the dominant radiative process, with a linewidth of only ϳ1 cm 21 . The temperature dependence of this new transition reveals a binding energy of 2.65 6 0.35 cm 21 , consistent with the spectroscopic value of 2.8 6 0.2 cm 21 and with theoretical predictions. This is to our knowledge the first experimental determination of the D 2 binding energy in unperturbed GaAs. [S0031-9007(98)05493-3] PACS numbers: 78.55. -m, 71.55. -i D 2 states in single-valley semiconductors, formed when a shallow neutral hydrogenic donor ͑D 0 ͒ binds a second electron, are the solid state analog of the negatively charged hydrogen ion ͑H 2 ͒. Such systems are of great interest, to a large extent because their small electron effective mass and large dielectric constants allow one, at least in principle, to investigate the plenitude of magnetic bound states predicted for the H 2 ion at much higher (by .10 4 and, thus, inaccessible) fields. While there have been many reports of D 2 centers in III-V semiconductors during the past decade, most are for quantum well (QW) samples, where two-dimensional (2D) effects increase the D 2 binding energy. The handful of studies [1-3] dealing with D 2 in bulk materials all involve significant binding energy enhancements due to magnetic fields. These early far infrared (FIR) investigations, albeit the first to identify D 2 states in bulk GaAs, suffered from a combination of materials and experimental technique-related problems which strictly limited these studies to the observation of relatively broad D 2 bands in a restricted number of compensated samples.As a result of these difficulties, recent effort has been focused on the study of 2D D 2 states in QW geometries, which also offer the possibility of engineering appropriate conditions for the creation of D 2 centers, via selective doping techniques [4][5][6][7]. While this has allowed D 2 centers to be identified in a less restricted variety of materials, the linewidths associated with the D 2 transitions observed in all of the existing FIR studies are still very broad, especially in comparison to the very small binding energy expected for D 2 in bulk GaAs [ϳ3.7 K or 2.6 cm 21 , where the effective Rydberg for neutral donors in GaAs is taken to be R ء 46.09 cm 21 (5.715 meV) [8] ] [9,10]. Further complications arise during the interpretation of QW FIR absorption spectra due to the possibility of confusing D 2 features with those arising from interexcited state neutral impurity transitions (from both well and barrier materials), as well as cyclotron resonance. Hence, identification of D 2 features in a given FIR absorption spectrum is not straightforward, relying on comparisons with quantitative theoretical predictions, and has often been controversial [1,[4][5][6][7]11].Recent advances in the purity of e...