Collect. Czech. Chem. Commun. 1985, 50, 1519-1536

Reduced double-minimum potential curves for XY3 pyramidal molecules

Vladimír Špirkoa, Svatopluk Civišb, Stanislav Berana, Petr Čárskya and Jürgen Fabianc

a The J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, 121 38 Prague 2, Czechoslovakia
b Department of Inorganic Chemistry, Charles University, 128 40 Prague 2, Czechoslovakia
c Department of Chemistry, Technical University of Dresden, 8027 Dresden, G.D.R.


The reduced potential curve (RPC) method used by Jenc and Pliva for studying the diatomic potentials is adapted for three-parameter studies of the inversional double-minimum potential functions of XY3 pyramidal molecules. Reduced double-minimum potential curves (RDMPC's) of the first, second and third row hydrides (CH3-, NH3, OH3+; SiH3-, PH3, SH3+; GeH3-, AsH3, SeH3+) are constructed using CNDO/2 and ab initio MBPT(2) theoretical potentials. The theoretical RDMPC's corresponding to a group of isoelectronic hydrides coincide to a high degree of approximation, so that they can be represented by a single curve. Furthermore, there is a nearly perfect coincidence between the theoretical RDMPC's of the first row hydrides and the ammonia experimental RDMPC (the only curve known experimentally). To illustrate a practical use of the proposed RPC approach, several approximants to the genuine phosphine potential are constructed (over a wide range of values for the inversion motion coordinate) by combining the available experimental data and the calculated RDMPC's. The resulting potentials exhibit a very close coincidence.