TY - JOUR
T1 - Ab initio band structure of polymethineimine isomers
AU - Jacquemin, Denis
AU - Champagne, Benoît
AU - André, Jean-Marie
PY - 1998/1/15
Y1 - 1998/1/15
N2 - Ab initio crystal orbital calculations have been performed on stereoregular polymethineimine (PMI) at the restricted Hartree-Fock/6-31G level. Since the optimized geometries of the parent oligomers show only small energy differences, four isomers, namely, trans-transoïd (TT), cis-transoïd (CT), trans-cisoïd (TC) and helical (HEL) have been studied to point out the geometry-dependences of the band structure, density of states (DOS) and polarizability. Some of these could be helpful for identifying the isomers. It turns out that the DOS makes the TT and CT isomers distinguishable, whereas the TC and HEL isomers present very similar DOS. Moreover, it is shown that the longitudinal polarizability per unit cell increases in the order HEL, TC, CT and TT.
AB - Ab initio crystal orbital calculations have been performed on stereoregular polymethineimine (PMI) at the restricted Hartree-Fock/6-31G level. Since the optimized geometries of the parent oligomers show only small energy differences, four isomers, namely, trans-transoïd (TT), cis-transoïd (CT), trans-cisoïd (TC) and helical (HEL) have been studied to point out the geometry-dependences of the band structure, density of states (DOS) and polarizability. Some of these could be helpful for identifying the isomers. It turns out that the DOS makes the TT and CT isomers distinguishable, whereas the TC and HEL isomers present very similar DOS. Moreover, it is shown that the longitudinal polarizability per unit cell increases in the order HEL, TC, CT and TT.
UR - http://www.scopus.com/inward/record.url?scp=0000619723&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0000619723
SN - 0021-9606
VL - 108
SP - 1023
EP - 1030
JO - The journal of chemical physics
JF - The journal of chemical physics
IS - 3
ER -