Excitonic effects in a time-dependent density functional theory

Igumenshchev, Kirill I.; Tretiak, Sergei; Chernyak, Vladimir Y.
September 2007
Journal of Chemical Physics;9/21/2007, Vol. 127 Issue 11, p114902
Academic Journal
Excited state properties of one-dimensional molecular materials are dominated by many-body interactions resulting in strongly bound confined excitons. These effects cannot be neglected or treated as a small perturbation and should be appropriately accounted for by electronic structure methodologies. We use adiabatic time-dependent density functional theory to investigate the electronic structure of one-dimensional organic semiconductors, conjugated polymers. Various commonly used functionals are applied to calculate the lowest singlet and triplet state energies and oscillator strengths of the poly(phenylenevinylene) and ladder-type (poly)(para-phenylene) oligomers. Local density approximations and gradient-corrected functionals cannot describe bound excitonic states due to lack of an effective attractive Coulomb interaction between photoexcited electrons and holes. In contrast, hybrid density functionals, which include long-range nonlocal and nonadiabatic corrections in a form of a fraction of Hartree-Fock exchange, are able to reproduce the excitonic effects. The resulting finite exciton sizes are strongly dependent on the amount of the orbital exchange included in the functional.


Related Articles

  • Cooperative versus dispersion effects: What is more important in an associated liquid such as water? Kirchner, Barbara // Journal of Chemical Physics;11/22/2005, Vol. 123 Issue 20, p204116 

    We implemented the quantum cluster equilibrium theory in our postprocessing program PEACEMAKER. This program may be run in conjunction with the very efficient vibrational frequency analysis code SNF and can therefore provide access to all electronic structure programs combined with this program....

  • Koopmans' multiconfigurational self-consistent field (MCSCF) Fukui functions and MCSCF perturbation theory. Gusarov, Sergey; Dmitriev, Yuri Yu.; Stoyanov, Stanislav R.; Kovalenko, Andriy // Canadian Journal of Chemistry;Aug2013, Vol. 91 Issue 9, p886 

    Prediction of chemical reactivity has become one of the highest priority tasks of computational chemistry since the development of the methods of modeling electronic structure. Despite the general simplicity of the physical concept of reactivity and the rapid development of modern density...

  • Chemical potential, hardness, hardness and softness kernel and locak hardness in the isomorphic... De Proft, Frank; Shubin Liu // Journal of Chemical Physics;8/22/1997, Vol. 107 Issue 8, p3000 

    Describes relations among reactivity descriptors within the modified isomorphic ensemble of density functional theory. Expressions for the softness and hardness kernel derived in the canonical, grand canonical, isomorphic and grand isomorphic ensemble; Response of the system's external...

  • A perturbative density functional theory of inhomogeneous fluid mixture. Choudhury, Niharendu; Ghosh, Swapan K. // Journal of Chemical Physics;5/1/1999, Vol. 110 Issue 17, p8628 

    Develops a simple perturbative density functional approach for an inhomogeneous fluid mixture based on a functional Taylor expansion of the free energy in terms of the density inhomogeneity up to third order. Proposal of an approximation for the three-body correlation function for the mixture;...

  • Electronic excitation in a syn-tetrasilane: 1,1,2,2,3,3, 4,4-octamethyltetrasilacyclopentane. Crespo, Raül; Piqueras, Mari; Michl, Josef // Theoretical Chemistry Accounts: Theory, Computation, & Modeling;Aug2007, Vol. 118 Issue 1, p81 

    We present a multistate complete active space second-order perturbation theory (MS-CASPT2) study of the low-lying valence excited states of a peralkylated tetrasilacyclopentane, c-(CH2Si4Me8) (1). The lowest-lying calculated valence excited states are located in the 37,400–50,500...

  • Simple preconditioning for time-dependent density functional perturbation theory. Lehtovaara, Lauri; Marques, Miguel A. L. // Journal of Chemical Physics;7/7/2011, Vol. 135 Issue 1, p014103 

    By far, the most common use of time-dependent density functional theory is in the linear-reponse regime, where it provides information about electronic excitations. Ideally, the linear-response equations should be solved by a method that avoids the use of the unoccupied Kohn-Sham states - such...

  • Ultrafast energy transfer from rigid, branched side-chains into a conjugated, alternating copolymer. Griffin, Graham B.; Lundin, Pamela M.; Rolczynski, Brian S.; Linkin, Alexander; McGillicuddy, Ryan D.; Zhenan Bao; Engel, Gregory S. // Journal of Chemical Physics;1/21/2014, Vol. 140 Issue 3, p1 

    We present the synthesis and characterization of a benzodithiophene/thiophene alternating copolymer decorated with rigid, singly branched pendant side chains. We characterize exciton migration and recombination dynamics in these molecules in tetrahydrofuran solution, using a combination of...

  • On the relationship between bond-length alternation and many-electron self-interaction error. Körzdörfer, Thomas; Parrish, Robert M.; Sears, John S.; Sherrill, C. David; Brédas, Jean-Luc // Journal of Chemical Physics;9/28/2012, Vol. 137 Issue 12, p124305 

    Predicting accurate bond-length alternations (BLAs) in long conjugated molecular chains has been a major challenge for electronic-structure theory for many decades. While Hartree-Fock (HF) overestimates BLA significantly, second-order perturbation theory and commonly used density functional...

  • Communication: An efficient analytic gradient theory for approximate spin projection methods. Hratchian, Hrant P. // Journal of Chemical Physics;Mar2013, Vol. 138 Issue 10, p101101 

    Spin polarized and broken symmetry density functional theory are popular approaches for treating the electronic structure of open shell systems. However, spin contamination can significantly affect the quality of predicted geometries and properties. One scheme for addressing this concern in...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics