Microwave and infrared characterization of several weakly bound NH3 complexesa)

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Abstract
We present the results of microwave and infrared spectroscopic studies of several van der Waals complexes of NH3. These results were obtained with a molecular beam electric resonance spectrometer. The microwave spectroscopy of the complexes (NH3)2 and Ar–NH3 show that both systems are nonrigid. The observed dipole moments for (NH3)2[0.74(2) D] and (ND3)2[0.57(1) D] are not compatible with the presently accepted theoretical structure. Ar–NH3, which has a complicated and currently unassigned microwave spectrum, exhibits Q branch inversion transitions near 19 GHz which indicate that the NH3 subunit is likely to be a near‐free rotor. Infrared studies of the complexes NH3–HCCH, NH3–CO2, (NH3)2, Ar–NH3, NH3–OCS, NH3–N2O, and NH3–HCN have been carried out with a line tunable CO2 laser. Only for NH3–HCN were no infrared resonances discovered. Photodissociative transitions are observed in all of the other systems. Band origins for the photodissociative infrared transitions involving the ν2 umbrella motion of NH3 were determined for NH3–HCCH [984.4(9) cm−1], NH3–CO2 [987.1(2) cm−1]. NH3–OCS [981.5(15) cm−1], and NH3–N2O [980(2) cm−1]. The observation of an infrared transition for Ar–NH3 at 938.69 cm−1, which is 40 cm−1 lower than the band origins in the other NH3 complexes, lends support to the model of Ar–NH3 mentioned above. NH3–HCCH, NH3–CO2, (NH3)2, and Ar–NH3 were studied in microwave‐infrared double resonance experiments in order to eliminate much of the inhomogeneous broadening present in their infrared spectra and to aid in the rotational assignment of the infrared spectra. Linewidths were determined for NH3–HCCH (0.15 GHz) and for NH3–CO2 [14(6) GHz]. An important result of this study is that the dissociation energies of all the complexes studied, except for NH3–HCN, are established to be less than 990 cm−1, i.e., 2.8 kcal/mol.