Electronic structure and excitations in oligoacenes from ab initio calculations
- 3 April 2006
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 124 (13), 134901
- https://doi.org/10.1063/1.2186999
Abstract
Oligoacenes C4n+2H2n+4 (n=2,…,6) are studied using a variety of ab initio methods. Density functional theory (DFT) optimized geometries were in good agreement with experiment. Vertical and adiabatic ionization potentials and electron affinities were computed with DFT and it was found that standard exchange-correlation (xc) functionals underestimate ionization potentials in oligoacenes. Possible reasons for this underestimation are discussed. Low lying electronic excitations were computed using time-dependent density functional theory, configuration interaction singles, and configuration interaction singles with approximate treatment of doubles. In agreement with earlier work, time-dependent DFT in conjunction with standard xc-energy functionals substantially underestimates the lowest (p) singlet-singlet electronic transition.Keywords
This publication has 52 references indexed in Scilit:
- Oligoacene exciton binding energies: Their dependence on molecular sizePhysical Review B, 2005
- Origin of the field-counteracting term of the Kohn-Sham exchange-correlation potential of molecular chains in an electric fieldPhysical Review A, 2000
- Solvent-induced stabilization of the naphthalene anion by water molecules: A negative cluster ion photoelectron spectroscopic studyThe Journal of Chemical Physics, 2000
- An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large moleculesThe Journal of Chemical Physics, 1998
- Bulk properties from finite-cluster calculations. VII. Accurate ab initio calculations on the Peierls distortions in polyaceneThe Journal of Chemical Physics, 1993
- Toward a systematic molecular orbital theory for excited statesThe Journal of Physical Chemistry, 1992
- Self-Consistent Equations Including Exchange and Correlation EffectsPhysical Review B, 1965
- Inhomogeneous Electron GasPhysical Review B, 1964
- The alternation of bond lengths in long conjugated molecules. - II. The polyacenesProceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences, 1960
- The alternation of bond lengths in long conjugated chain moleculesProceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences, 1959