TY - JOUR
T1 - Ab initio calculations of the ground electronic states of polyiodide anions
AU - Sharp, Stephanie B.
AU - Gellene, Gregory I.
PY - 1997/3/13
Y1 - 1997/3/13
N2 - Equilibrium bond lengths, harmonic frequencies, electron affinities, and dissociation energies (as appropriate) were determined for I, I-,I2,I2-, and I3- by CCSD(T) and four DFT methods (BLYP, BPW91, B3LYP, and B3PW91) using a basis set consisting of a relativistic effective core potential and a triple-zeta plus 2df polarization functions (ECP-TZ(2df)) for the valence electrons. Comparison of the DFT results with the CCSD(T) results and available experimental information indicates that the B3PW91 approach does particularly well describing the bonding in these species. B3PW91/ECP-TZ(2df) calculations of I5- in linear (D∞h) and bent (C2v,) geometries indicate that the linear structure is a low-energy transition state lying only about 0.1-0.2 eV above the C2v global minimum-energy structure. Harmonic frequencies and infrared and Raman intensities are calculated for both structures and compared to available experimental information.
AB - Equilibrium bond lengths, harmonic frequencies, electron affinities, and dissociation energies (as appropriate) were determined for I, I-,I2,I2-, and I3- by CCSD(T) and four DFT methods (BLYP, BPW91, B3LYP, and B3PW91) using a basis set consisting of a relativistic effective core potential and a triple-zeta plus 2df polarization functions (ECP-TZ(2df)) for the valence electrons. Comparison of the DFT results with the CCSD(T) results and available experimental information indicates that the B3PW91 approach does particularly well describing the bonding in these species. B3PW91/ECP-TZ(2df) calculations of I5- in linear (D∞h) and bent (C2v,) geometries indicate that the linear structure is a low-energy transition state lying only about 0.1-0.2 eV above the C2v global minimum-energy structure. Harmonic frequencies and infrared and Raman intensities are calculated for both structures and compared to available experimental information.
UR - http://www.scopus.com/inward/record.url?scp=0031095142&partnerID=8YFLogxK
U2 - 10.1021/jp962755r
DO - 10.1021/jp962755r
M3 - Article
AN - SCOPUS:0031095142
SN - 1089-5639
VL - 101
SP - 2192
EP - 2197
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 11
ER -