Artículo
A quartic force field coordinate substitution scheme using hyperbolic sine coordinates
Fecha de publicación:
08/2017
Editorial:
John Wiley & Sons
Revista:
International Journal of Quantum Chemistry
ISSN:
0020-7608
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Quartic force fields (QFF) are currently the most cost-effective method for the approximation of potential energy surfaces for the calculation of anharmonic vibrational energies. It is known, although, that its performance can be less than satisfactory due to limitations related to slow convergence of the series. In this article, we present a coordinate substitution scheme using a combination of Morse and sinh coordinates, well adapted for its use with cartesian normal coordinates. We derive expressions for analytical integrals for use in VSCF and VCI calculations and show that the simultaneous substitution of symmetric and antisymmetric normal coordinates by Morse and sinh coordinates, respectively, significantly improves the vibrational transition frequencies for these modes in a well-balanced fashion. The accuracy of this substitution scheme is demonstrated by comparing one and two-dimensional sections of substituted and unsubstituted QFF with ab initio potential energy grids, as well as with vibrational energy calculations using as test cases two well-studied benchmark molecules: water and formaldehyde. We conclude that the coordinate substitution scheme presented constitutes a very attractive alternative to simple QFFs in the context of cartesian normal coordinates.
Palabras clave:
QUANTUM CHEMISTRY
,
QUARTIC FORCE FIELDS
,
VIBRATIONAL STRUCTURE
Archivos asociados
Licencia
Identificadores
Colecciones
Articulos(INQUIMAE)
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos(INQUINOA)
Articulos de INST.DE QUIMICA DEL NOROESTE
Articulos de INST.DE QUIMICA DEL NOROESTE
Citación
Alonso de Armiño, Diego Javier; Bustamante, Carlos Mauricio; A quartic force field coordinate substitution scheme using hyperbolic sine coordinates; John Wiley & Sons; International Journal of Quantum Chemistry; 117; 15; 8-2017; 1-11
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