Vibrational spectra of polyatomic molecules are often obtained from a polynomial expansion of the adiabatic potential around a minimum. For several molecules, we show that such an approximation displays an unphysical saddle point of comparatively small energy, leading to a region where the potential is negative and unbounded. This poses an upper limit for a reliable evaluation of vibrational levels. We argue that the presence Of Such saddle points is general.

Low-energy unphysical saddle in polynomial molecular potentials / A. Del Monte, N. Manini, L.G. Molinari, G.P. Brivio. - In: MOLECULAR PHYSICS. - ISSN 0026-8976. - 103:5(2005), pp. 689-696.

Low-energy unphysical saddle in polynomial molecular potentials

N. Manini
Secondo
;
L.G. Molinari
Penultimo
;
2005

Abstract

Vibrational spectra of polyatomic molecules are often obtained from a polynomial expansion of the adiabatic potential around a minimum. For several molecules, we show that such an approximation displays an unphysical saddle point of comparatively small energy, leading to a region where the potential is negative and unbounded. This poses an upper limit for a reliable evaluation of vibrational levels. We argue that the presence Of Such saddle points is general.
ANHARMONIC-FORCE FIELD; INTRAMOLECULAR VIBRATIONAL-RELAXATION; DENSITY-FUNCTIONAL THEORY; POLYATOMIC-MOLECULES; BENZENE; STATE; CONSTANTS; RESONANCE; CONTINUUM; SURFACES
Settore FIS/02 - Fisica Teorica, Modelli e Metodi Matematici
Settore FIS/03 - Fisica della Materia
2005
Article (author)
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/6121
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