Vibrational spectrum of the H5+ molecule using quantum Monte Carlo

Physics – Chemical Physics

Scientific paper

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9 pages, 3 figures and 2 tables

Scientific paper

In this article we present a caracterization of the vibrational spectrum of the H5+ molecule using the correlation function quantum Monte Carlo (CFQMC) method and a genetic algorithm study of the topology of the potential energy surface used in this work. The vibrational modes associated with the H3+ - H2 torsion and stretching posses very flat minima. As a consequence the fundamental frequencies corresponding to these modes are poorly described in the harmonic approximation. The vibrational frequencies obtained in this work are in good agreement with the available experimental data as well as other computational methods found in literature. In our genetic algorithm study of the potential energy surface using cartesian coordinates we have found some unexpected minima. A careful analysis shows that some of these minima are described by the same curviliniar coordinates in which the potential is described. However, they represent nonequivalent molecular geometries.

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