The infrared (IR) spectrum of the ammoniated ammonium dimer, is more complex than those of the larger protonated ammonia clusters due to close-lying fundamental and combination bands and possible Fermi resonances (FR). To date, the only theoretical analysis involved partial dimensionality quantum nuclear dynamic simulations, assuming a symmetric structure (D-3d) with the proton midway between the two nitrogen atoms. Here we report an extensive study of the less symmetric (C-3v) dimer, utilizing both second order vibrational perturbation theory (VPT2) and ab initio molecular dynamics (AIMD), from which we calculated the Fourier transform (FT) of the dipole-moment autocorrelation function (DACF). The resultant IR spectrum was assigned using FTed velocity autocorrelation functions (VACFs) of several interatomic distances and angles. At 50 K, we have been able to assign all 21 AIMD fundamentals, in reasonable agreement with MP2-based VPT2, about 30 AIMD combination bands, and a difference band. The combinations involve a wag or the NN stretch as one of the components, and appear to follow symmetry selection rules. On this basis, we suggest possible assignments of the experimental spectrum. The VACF-analysis revealed two possible FR hands, one of which is the strongest peak in the computed spectrum. Raising the temperature to 180 K eliminated the "proton transfer mode" (PTM) fundamental, and reduced the number of Observed combination bands and FRs. With increasing temperature, fundamentals red-shift, and the doubly degenerate wags exhibit larger anharmonic splittings in their VACF bending spectra. We have repeated the analysis for the H3ND+NH3 isotopologue, finding that it has a simplified spectrum, with all the strong peaks being fundamentals. Experimental study of this isotopologue may thus provide a good starting point for disentangling the N2H7+ spectrum.
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