Anharmonic Potential Functions in Polyatomic Molecules as Derived from Their Vibrational and Rotational Spectra

It is well known that the anharmonic part of the molecular potential function contributes to the vibration-rotation energy and to the apparent molecular geometry, although the anharmonic effect is not so profound as that from its harmonic counterpart. Nevertheless, it cannot simply be ignored for the precise treatment of molecular dynamics and structures. For a better understanding of the molecular potential function, it is highly desirable to extend the force constant calculation to evaluate the terms beyond quadratic, which will give a more realistic potential map of polyatomic molecules for wider ranges of atomic displacements. The vibrational anharmonicity also affects the transition intensities through the mixing vibration-rotation wave functions.