Low-lying excitations of poly-fused thiophene within Pariser-Parr-Pople model: A density matrix renormalization group study.
We studied the nature of the ground and low-lying excited states of poly-fused thiophene oligomers within long-range Pariser-Parr-Pople (PPP) model Hamiltonian with up to 14 monomers using symmetrized density matrix renormalization group technique. Our results show that the lowest dipole-allowed state lies below the lowest dipole forbidden two-photon state, indicating that poly-fused thiophenes are strongly fluorescent. The lowest triplet state lies below the two-photon state, which is in agreement with the general trend in conjugated polymers. The charge density and bond order calculations of three low-lying excited states, along with the ground state of fused thiophene oligomers, show a significant transfer of charge from sulfur to adjacent carbon atom in the middle of the largest system size and these excitations are localized. The charge density and bond order calculations on singly and doubly doped states show that bipolarons are not stable entity in these systems. The calculations of low-lying excitations on radical cation and anion of fused thiophene oligomers show a new energy band in the low energy region, which is strongly coupled to its hole and electron conductivity. This implies that poly-fused thiophenes posses novel field-effect transistor properties.
Das
Mousumi
M
Department of Chemical Sciences, Indian Institute of Science Education and Research, Kolkata, Mohanpur Campus, Mohanpur 741252, Nadia, West Bengal, India. mousumi@iiserkol.ac.in
D000465:Algorithms; D004553:Electric Conductivity; D015394:Molecular Structure; D011789:Quantum Theory; D013876:Thiophenes / Q000737:chemistry*
D013876:Thiophenes