TY - JOUR
T1 - Charge distributions in polyacetylene chains containing a positively charged defect
AU - Monev, Valentin
AU - Spassova, Milena
AU - Champagne, Benoît
PY - 2005/8/15
Y1 - 2005/8/15
N2 - We present a comparative study of the AIM, CHELPG, GAPT, MK, Mulliken, NPA, and RESP charge distributions associated with a positively charged soliton on increasingly large trans-polyacerylene chains, at HF, MP2, and DFT levels of theory. The charge storage in the soliton-bearing systems is explored in detail, including charge magnitude, charge separation, charge alternation, and chain length effects. The grouping of the charge distributions at a given level of theory, as well as the sensitivity of a given charge distribution to the inclusion of electron correlation in its computation, are investigated using similarity analysis. Several of the charge definitions have been applied for the first time for charged soliton-bearing systems, and there are substantial differences between the charge distributions for the charged and neutral systems. Thus, AIM charges are no longer one of the largest charge values, the AIM charges can be in counterphase with other definitions, and the GAPT charges for neutral systems are quite different from the GAPT charges for charged systems, e.g., the magnitudes of the GAPT charges are anomalously large and increase with the size of the charged system.
AB - We present a comparative study of the AIM, CHELPG, GAPT, MK, Mulliken, NPA, and RESP charge distributions associated with a positively charged soliton on increasingly large trans-polyacerylene chains, at HF, MP2, and DFT levels of theory. The charge storage in the soliton-bearing systems is explored in detail, including charge magnitude, charge separation, charge alternation, and chain length effects. The grouping of the charge distributions at a given level of theory, as well as the sensitivity of a given charge distribution to the inclusion of electron correlation in its computation, are investigated using similarity analysis. Several of the charge definitions have been applied for the first time for charged soliton-bearing systems, and there are substantial differences between the charge distributions for the charged and neutral systems. Thus, AIM charges are no longer one of the largest charge values, the AIM charges can be in counterphase with other definitions, and the GAPT charges for neutral systems are quite different from the GAPT charges for charged systems, e.g., the magnitudes of the GAPT charges are anomalously large and increase with the size of the charged system.
KW - Charge distribution
KW - Charged soliton
KW - Similarity analysis
KW - Trans-polyacetylene
UR - http://www.scopus.com/inward/record.url?scp=23144463177&partnerID=8YFLogxK
U2 - 10.1002/qua.20605
DO - 10.1002/qua.20605
M3 - Article
AN - SCOPUS:23144463177
SN - 0020-7608
VL - 104
SP - 354
EP - 366
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
IS - 3
ER -