Canonical Potentials and Spectra within the Born–Oppenheimer Approximation Academic Article uri icon

abstract

  • A generalized formulation of canonical transformations and spectra are used to investigate the concept of a canonical potential strictly within the Born-Oppenheimer approximation. Data for the most accurate available ground electronic state pairwise intermolecular potentials in H2, HD, D2, HeH(+), and LiH are used to rigorously evaluate such transformations. The corresponding potentials are generated explicitly using parameters calculated with algebraic functions from that of the single canonical potential of the simplest molecule, H2(+). The efficacy of this approach is further tested by direct comparison of the predicted eigenvalues of all vibrational states in the selected molecular systems considered with the corresponding most accurately known Born-Oppenheimer eigenvalues currently available. Deviations are demonstrated to be less than 2 cm(-1) for all vibrational states in H2, HD, D2, HeH(+), and LiH, with an average standard deviation of 0.27 cm(-1) for the 87 states considered. The implications of these results for molecular quantum chemistry are discussed.

author list (cited authors)

  • Walton, J. R., Rivera-Rivera, L. A., Lucchese, R. R., & Bevan, J. W.

publication date

  • January 1, 2015 11:11 AM