Ab initio theoretical study of the methyl and phosphine torsion modes in ethylphosphine

In this paper, the far infrared (FIR) methyl and phosphine torsional frequencies and intensities are determined theoretically in ethylphosphine from ab initio calculations. For this purpose, the potential energy function for the double rotation of the methyl and phosphine groups in the electronic ground state is determined in a standard calculation by using the MP2/RHF and a 6-31G(3df,p) basis set, with full optimization of the geometry. The numerical results are fitted to a symmetry adapted analytical form and introduced together with the kinetic parameters into the Hamiltonian operator. The Schrödinger equation for these two motions is solved by developing the solutions on the basis of products of trigonometric functions. From the energy levels, the torsional functions and the dipole moment variations the FIR spectrum is synthesized. A new assignment is proposed for some trans-trans and the gauche-gauche transitions between the phosphine levels. Additional transitions between the methyl levels are also proposed. It is concluded that a two dimensional calculation is indispensable for reproducing the FIR torsional spectrum in the region from 200 to 140 cm-1. © 1997 American Institute of Physics.This work has been supported by the European Union under Contract No. CHRZ CT 93-0157 into the Human Capital and Mobility Scheme. The authors also acknowledge the nancial assistance of the ‘‘Comision Interministerial de Ciencias y Tecnologia’’ of Spain through Grant No. PB 93- 0185.Peer Reviewe