Multidimensional Hamiltonian for tunneling with position-dependent mass
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Título: | Multidimensional Hamiltonian for tunneling with position-dependent mass |
Autor/a: | Fernández-Ramos, Antonio Smedarchina, Zorka Siebrand, Willem |
Centro/Departamento: | Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares Universidade de Santiago de Compostela. Departamento de Química Física |
Data: | 2014-09-15 |
Editor: | APS Physics |
Cita bibliográfica: | Fernández-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 |
Resumo: | A 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 |
Versión do editor: | https://doi.org/10.1103/PhysRevE.90.033306 |
URI: | http://hdl.handle.net/10347/16855 |
DOI: | 10.1103/PhysRevE.90.033306 |
ISSN: | 2470-0045 |
E-ISSN: | 2470-0053 |
Dereitos: | ©2014 American Physical Society |
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