"Triplet-excited region" in polyene oligomers revisited: Pariser-Parr-Pople model studied with the density matrix renormalization group method.
We have carried out density matrix renormalization group calculations on the T1 state of linear polyenes applying the Pariser-Parr-Pople (PPP) Model. The geometry optimization for the polyene oligomers C(2n)H(2n+2) (n = 4,5,6,...,15) shows that the S0 to T1 excitation region is composed of a soliton-antisoliton pair located symmetrically away from the center of the chain and leads to single- and double-bond interconversions in between. The distance between the soliton and antisoliton centers in T1 state changes with the length of the chain, contradictory to earlier conclusions obtained with PPP-SDCI or ab initio SCI methods. The inconsistency most possibly comes from the insufficient consideration of the electron correlations in small-scale CI methods.
Institute of Theoretical and Computational Chemistry, Department of Chemistry, Nanjing University, Nanjing, 210093, China.
Haibo
H
Ma
Chungen
C
Liu
Yuansheng
Y
Jiang