Validity of the minimum polarizability principle in molecular vibrations and internal rotations: An ab initio SCF study
Author
dc.contributor.author
Chattaraj, Pratim K.
Author
dc.contributor.author
Fuentealba Rosas, Patricio
Author
dc.contributor.author
Jaque, Pablo
Author
dc.contributor.author
Toro Labbé, Alejandro
Admission date
dc.date.accessioned
2018-12-20T14:41:17Z
Available date
dc.date.available
2018-12-20T14:41:17Z
Publication date
dc.date.issued
1999
Cita de ítem
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Journal of Physical Chemistry A, Volumen 103, Issue 46, 2018, Pages 9307-9312
Identifier
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10895639
Identifier
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10.1021/jp9918656
Identifier
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https://repositorio.uchile.cl/handle/2250/157043
Abstract
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Molecular vibrations in ammonia (NH3) and hydrogen sulfide (H2S), and internal rotations in hydrogen peroxide (HOOH), hydrogen thioperoxide (HSOH), hydrogen persulfide (HSSH), and ethylene (C2H4) are studied using ab initio SCF methods at the Hartree-Fock level using a standard Pople 6-311G** basis set. Polarizability values are calculated using both Pople's and Sadlej's basis sets. Any nontotally symmetric distortion in bond length or bond angle along the vibrational symmetry coordinates of a molecule around its equilibrium geometry decreases the equilibrium hardness value and increases the equilibrium polarizability value. During rotational isomerization the minimum energy conformation corresponds to the maximum hardness and minimum polarizability values and the maximum energy conformation corresponds to the minimum hardness and maximum polarizability values. Density functional calculations confirm these observed trends. In general we have found that the conditions of maximum hardnes