Quantum Monte Carlo and genetic algorithm study of the potential energy surface of the H molecule

Abstract

AbstractIn this article we present a characterization of the vibrational spectrum of the H molecule using the correlation function quantum Monte Carlo (CFQMC) method and a genetic algorithm study of the topology of the potential energy surface (PES) used. The vibrational modes associated with the H‐H2 torsion and stretching possess very flat minima. As a consequence the fundamental frequencies corresponding to these modes are poorly described in the harmonic approximation. In our genetic algorithm study of the PES using Cartesian coordinates we have found some unexpected minima. A careful analysis shows that, in the curvilinear coordinates in which the potential is described, some of these minima have identical coordinates. Nevertheless, they represent nonequivalent molecular geometries. The vibrational frequencies obtained in this work are not in good agreement with available experimental data as well as other computational methods. It shows that our method of detailed analysis of PESs could reveal shortcomings introduced by the use of curvilinear coordinates. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008