Quantum mechanics of the anharmonic oscillator

Abstract

SummaryA method is presented for the accurate numerical treatment of molecular vibration problems in which the potential energy function is of the formThe treatment is carried through in detail for the case V(q) = Aq2 + Bq4, which, in most instances affords an adequate description of the potential. There is no restriction on the relative magnitudes of quadratic and quartic terms so that the method is equally applicable to the purely anharmonic oscillations occurring in types of ring bending (1), where V(q) = aq4.An approximate formula is derived for the energy levels in the general case. The case V = aq4 affords an illustration of the accurate treatment; the first five eigen-values and eigen-functions are computed and from them the associated transitionprobabilities. Numerical results are presented in a form convenient for further application. On comparison the approximate formula is found to yield results in error by approximately 1 %, the error decreasing for the higher levels for which the formula tends to a B.W.K. expression. In conclusion a ground-state eigen-function of simple analytical form is found to approximate remarkably well to the case of purely quartic vibrations.