Structure, internal mobility, and spectrum of the ammonia dimer: Calculation of the vibration–rotation-tunneling states

• Published in: The Journal of chemical physics 1994-11, Vol.101 (10), p.8430-8442
• Main Authors: Olthof, E. H. T., van der Avoird, A., Wormer, P. E. S.
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.468105

We have obtained a potential for (NH3)2 by calculating the six-dimensional vibra- tion–rotation-tunneling (VRT) states from a model potential with some variable parameters, and adjusting some calculated transition frequencies to the observed far-infrared spectrum. The equilibrium geometry is strongly bent away from a linear hydrogen bonded structure. Equivalent minima with the proton donor and acceptor interchanged are separated by a barrier of only 7 cm−1. The barriers to rotation of the monomers about their C3 axes are much higher. The VRT levels from this potential agree to about 0.25 cm−1 with all far-infrared frequencies of (NH3)2 observed for K=0, ‖K‖=1, and ‖K‖=2 and for all the symmetry species: Ai=ortho–ortho, Ei=para–para, and G=ortho–para. Moreover, the dipole moments and the nuclear quadrupole splittings agree well with the values that are observed for the G states. The potential has been explicitly transformed to the center-of-mass coordinates of (ND3)2 and used to study the effects of the deuteration on the VRT states. The observed decrease of the dipole moment and the (small) changes in the nuclear quadrupole splittings are well reproduced. It follows from our calculations that the ammonia dimer is highly nonrigid and that vibrational averaging effects are essential. Seemingly contradictory effects of this averaging on its properties are the consequence of the different hindered rotor behavior of ortho and para monomers.