Study of the Ambiguity of Effective Hamiltonian for the Fundamental Degenerate States V3 of the Molecule 12CD4

Authors: Ouardi Okkacha, Kaarour Abedlkrim, Meskine Mohamed

Abstract:

The effective Hamiltonians are widely used in molecular spectroscopy for the interpretation of the vibration-rotation spectra. Their construction is an ambiguous procedure due to the existence of unitary transformations that change the effective Hamiltonian but do not change its eigenvalues. As a consequence of this ambiguity, it may happen that some parameters of effective Hamiltonians cannot be recovered from experimental data in a unique way. The type of admissible transformations which keeps the operator form of the effective Hamiltonian unaltered and the number of empirically determinable parameters strongly depend on the symmetry type of a molecule (asymmetric top, spherical top, and so on) and on the degeneracy of the vibrational state. In this work, we report the study of the ambiguity of effective Hamiltonian for the fundamental degenerate states v3 of the Molecule 12CD4.

Keywords: 12CD4, high-resolution infrared spectra, tetrahedral tensorial formalism, vibrational states, rovibrational line position analysis, XTDS, SPVIEW