Potential Function for the Inversion Process of Ammonia
- 1 December 1966
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 45 (11), 4303-4309
- https://doi.org/10.1063/1.1727489
Abstract
The process of inversion of ammonia has been considered as described by two totally symmetric internal coordinates. The potential function has been chosen by theoretical considerations and the values of the parameters which appear in it have been fixed by minimizing the differences between the calculated eigenvalues of the vibrational problem and the known values of the observed frequencies. Two versions of the vibrational problem have been considered; a simplified one (monodimensional), where only the bond angles are allowed to change, and a complete two‐dimensional one where the bond lengths were also allowed to change. The potential functions so obtained give a fairly good agreement between calculated and observed frequencies. The two‐dimensional potential function has the minimum at a bond length of 1.878 a.u. and at a bond angle of 105°36′ and gives a value of 0.00905 a.u. as the potential barrier to inversion. The bond length for the minimum of energy at the planar configuration is 1.837 a.u. This potential function and the resulting eigenfunctions of the vibrational Hamiltonian have been employed to calculate some spectroscopic constants, such as the quadratic and cubic force constants related to two totally symmetric coordinates, and the differences between the rotational constants of the odd and the even levels. The agreement with the available experimental data is satisfactory. Results of the above calculations are also given for ND3.Keywords
This publication has 10 references indexed in Scilit:
- Extended Hartree—Fock Wavefunctions: Optimized Valence Configurations for H2 and Li2, Optimized Double Configurations for F2The Journal of Chemical Physics, 1966
- Theoretical calculation of the vibrational spectra of some XHn type moleculesTheoretical Chemistry Accounts, 1966
- Self-Consistent-Field Wavefunctions and Computed Potential-Energy Curves for the NH3 and NH Molecules, in One-Center ApproximationThe Journal of Chemical Physics, 1965
- The calculation of force constants and normal coordinates—IV XH4 and XH3 moleculesSpectrochimica Acta, 1964
- The anharmonicity correction for polyatomic moleculesJournal of Molecular Spectroscopy, 1964
- Potential Function for the Inversion of AmmoniaThe Journal of Chemical Physics, 1962
- Inversion-vibration and inversion-rotation interactions in the ammonia moleculeJournal of Molecular Spectroscopy, 1962
- United Atom Treatment of the Behavior of Potential Energy Surfaces of Polyatomic Molecules at Small Internuclear DistancesThe Journal of Chemical Physics, 1959
- VIBRATION–ROTATION BANDS OF AMMONIA: II. THE MOLECULAR DIMENSIONS AND HARMONIC FREQUENCIES OF AMMONIA AND DEUTERATED AMMONIACanadian Journal of Physics, 1957
- Absolute Infrared Intensities of Vibration Bands in Ammonia and PhosphineThe Journal of Chemical Physics, 1956