Vibration energy levels of the PH3, PH2D, and PHD2 molecules calculated from high order potential energy surface

Abstract

Vibrational energy levels of the PH(3), PH(2)D, and PHD(2) molecules were calculated from the new extended potential energy surface (PES) determined in this work. The coupled-cluster approach with the perturbative inclusion of the connected triple excitations CCSD(T) and correlation consistent polarized valence basis set cc-pV5Z was employed in the ab initio calculations of electronic ground state energies. The contribution of relativistic effects to the overall electronic energy surface was computed using quasirelativistic mass-velocity-Darwin approach. These ab initio points were fitted by a parametrized function with one parameter empirically adjusted. The grid of 11,697 geometrical nuclear configurations covers a large domain of the six dimensional internal coordinate space and was designed to provide vibration energy levels of phosphine molecule up to 7000 cm(-1) above the zero point vibration energy with reasonable accuracy. The analytical representation of the PES was determined through the expansion in symmetry adapted products of nonlinear internal coordinates for various orders of analytical expansions up to the tenth order. The dependence of calculated vibration energy levels on the analytical representation of PES and on the coordinate choice was studied. Calculated vibration levels are in very good agreement with observations: The root mean squares deviation between theoretically calculated and observed band centers is 1.4 cm(-1) for PH(3), 0.4 cm(-1) for PH(2)D, and 0.6 cm(-1) for PHD(2).