Application Of B-Splines In Determining The Eigenspectrum Of Diatomic Molecules: Robust Numerical Description Of Halo-State And Feshbach Molecules

The B-spline basis-set method is applied to determining the rovibrational eigenspectrum of diatomic molecules. Particular attention is paid to a challenging numerical task of an accurate and efficient description of the vibrational levels near the dissociation limit (halo-state and Feshbach molecules). Advantages of using B-splines are highlighted by comparing the performance of the method with that of the commonly used discrete-variable representation (DVR) approach. Several model cases, including the Morse potential and realistic potentials with 1/R-3 and 1/R-6 long-range dependence of the internuclear separation are studied. We find that the B-spline method is superior to the DVR approach and it is robust enough to properly describe the Feshbach molecules. The developed numerical method is applied to studying the universal relation of the energy of the last bound state to the scattering length. We illustrate numerically the validity of the quantum-defect-theoretic formulation of such a relation for a 1/R-6 potential.