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The Born-Oppenheimer Approximation Revisited

         

摘要

We present an improved Born-Oppenheimer method for the treatment of molecules. Our development is based on taking into account a portion of the kinetic energy which was inadvertently omitted by Born and Oppenheimer. Our theory replaces the set of standard atom-atom potentials by an evolution operator. In particular, in contrast to the traditional Born-Oppenheimer method our amended basis describes the so-called Wannier phenomenon which deforms potential surfaces, and traps one or more threshold electrons into an unstable equilibrium. Within our framework that trapping manifests itself as a Fresnel distribution. Finally we discover a π/2 phase jump in the evolution operator caused by the diffraction of a two-electron wave from a potential ridge.

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