Semiclassical path integral theory of a double‐well potential in an electric field

Abstract

AbstractA recently published methodology based on semiclassical path integral (SCPI) theory was implemented in the case of a model of a double‐well potential perturbed by a static electric field, with application to the inversion frequency of NH3. This model was chosen as an idealized case for testing of the present approach, as well as for quantum mechanical models that might be applied in the future. The calculations were concerned with the variation of the frequency of inversion as a function of field strength, F, and of distance, xf (from the symmetric point xo = 0), where the field is “felt.” It is found that this variation occurs sharply in very small regions of values of these parameters, and the system switches from internal oscillation to diffusion to the continuum. The fact that the theory is in analytic form allows the extraction of results and conclusions not only at the full SCPI level, but also at the Jeffreys–Wentzel–Kramers–Brillouin (JWKB) level. Comparison shows that the discrepancy sets in as the field strength increases, in accordance with the well‐known limitations of the JWKB method regarding its dependence on the degree of variation of the potential as a function of position. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006