TY - JOUR
T1 - Validity of the minimum polarizability principle in molecular vibrations and internal rotations
T2 - An ab initio SCF study
AU - Chattaraj, Pratim K.
AU - Fuentealba, Patricio
AU - Jaque, Pablo
AU - Toro-Labbé, Alejandro
PY - 1999/11/18
Y1 - 1999/11/18
N2 - 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 hardness and minimum polarizability complement the minimum energy criterion for molecular stability.
AB - 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 hardness and minimum polarizability complement the minimum energy criterion for molecular stability.
UR - http://www.scopus.com/inward/record.url?scp=0001660918&partnerID=8YFLogxK
U2 - 10.1021/jp9918656
DO - 10.1021/jp9918656
M3 - Article
AN - SCOPUS:0001660918
VL - 103
SP - 9307
EP - 9312
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 46
ER -