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dc.contributor.authorFernández-Ramos, Antonio
dc.contributor.authorSmedarchina, Zorka
dc.contributor.authorSiebrand, Willem
dc.identifier.citationFernández-Ramos, A., Smedarchina, Z., & Siebrand, W. (2014). Multidimensional Hamiltonian for tunneling with position-dependent mass. Physical Review E, 90(3). doi: 10.1103/physreve.90.033306
dc.description.abstractA multidimensional Hamiltonian for tunneling is formulated, based on the mode with imaginary frequency of the transition state as a reaction coordinate. To prepare it for diagonalization, it is transformed into a lower-dimension Hamiltonian by incorporating modes that move faster than the tunneling into a coordinate-dependent kinetic energy operator, for which a Hermitian form is chosen and tested for stability of the eigenvalues. After transformation to a three-dimensional form, which includes two normal modes strongly coupled to the tunneling mode, this Hamiltonian is diagonalized in terms of a basis set of harmonic oscillator functions centered at the transition state. This involves a sparse matrix which is easily partially diagonalized to yield tunneling splittings for the zero-point level and the two fundamental levels of the coupled modes. The method is tested on the well-known benchmark molecule malonaldehyde and a deuterium isotopomer, for which these splittings have been measured. Satisfactory agreement with experiment results is obtained
dc.publisherAPS Physics
dc.rights©2014 American Physical Society
dc.titleMultidimensional Hamiltonian for tunneling with position-dependent mass
dc.contributor.affiliationUniversidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares
dc.contributor.affiliationUniversidade de Santiago de Compostela. Departamento de Química Física

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