The Vibrational Stretching States of the Pyramidal Molecules: Application to the Arsine and Stibine.

Study of the stretching modes of the arsine molecule

Abstract To study local mode XY 3 molecules, we use properties of the group chain U ( 4 ) ⊃ U ( 3 ) ⊃ K ( 3 ) ⊃ S ( 3 ) ≈ C 3 v . For the Hamiltonian, we deduce diagonal terms and coupling terms between bonds. We analyze the stretching modes of the arsine molecule. An algebraic transition operator is built and applied to the same molecular system.

Expressions of Effective Hamiltonian Parameters of XY4 Molecules in the Tetrahedral Formalism

We have derived expressions of second-order effective Hamiltonian parameters of XY4 molecules in the tetrahedral formalism (1992, J. P. Champion et al., "Spectroscopy of the Earth's Atmosphere and Interstellar Medium: Spherical Top Spectra," Academic Press, San Diego). They are written as a function of the force constants of the potential expanded in terms of the dimensionless normal coordinates. These expressions can be used in the isolated band scheme as well as in the polyad one. The ambiguity of the effective Hamiltonian parameters is treated. Relations between the parameters for q2 and q4 terms and Hecht's anharmonicity constants (1960, K. T. Hecht, J. Mol. Spectrosc. 5, 355-389) in th…