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arxiv: 0805.4526 · v1 · submitted 2008-05-29 · 🧮 math-ph · math.MP

A Mathematical Theory for Vibrational Levels Associated with Hydrogen Bonds II: The Non--Symmetric Case

classification 🧮 math-ph math.MP
keywords hydrogenvibrationalapproximationbondsborn--oppenheimerdescribedifferentepsilon
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We propose an alternative to the usual time--independent Born--Oppenheimer approximation that is specifically designed to describe molecules with non--symmetrical hydrogen bonds. In our approach, the masses of the hydrogen nuclei are scaled differently from those of the heavier nuclei, and we employ a specialized form for the electron energy level surface. As a result, the different vibrational modes appear at different orders of approximation. Although we develop a general theory, our analysis is motivated by an examination of the F H Cl- ion. We describe our results for it in detail. We prove the existence of quasimodes and quasienergies for the nuclear vibrational and rotational motion to arbitrary order in the Born--Oppenheimer parameter epsilon. When the electronic motion is also included, we provide simple formulas for the quasienergies up to order epsilon cubed that compare well with experiment and numerical results.

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