The infrared spectrum of PF3 and analysis of rotational energy clustering effect

Abstract

The first variational calculations of the rotational-vibrational levels of PF are performed and intensities for dipole transitions between them computed. This is accomplished using new state of the art potential energy and dipole moment surfaces. This allows the infrared spectrum of PF to be simulated, providing a complete overview of the ro-vibrational spectrum up to J=100 in the wavenumber range 0–3100 cm−1. The behaviour of PF at high rotational excitations is also investigated. The formation of quasi-degenerate 6-fold rotational energy clusters at high rotational excitation are investigated up to J=270 and are found to occur around J=200. The clustering effect is analysed in terms of semi-classical rotational energy surfaces.