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Title: An analytic mapping of oligomer potential energy surfaces to an effective Frenkel model

Abstract

While the use of Frenkel-type models for semiconducting polymer assemblies and related molecular aggregates is well established, the direct parametrization of such models based on electronic structure data is attempted less frequently. In this work, we develop a systematic mapping procedure which is adapted to J-type and H-type homo-aggregate systems. The procedure is based upon the analytic solution of an inverse eigenvalue problem for an effective Frenkel Hamiltonian with nearest-neighbor couplings. Vibronic interactions are included for both site-local and site-correlated modes. For illustration, an application is presented to the excited-state ab initio potential energy surfaces (PESs) of an oligothiophene octamer. The procedure performs a pointwise mapping of the PESs of oligomers of arbitrary chain length n, provided that the electronic ground state and any two of the n lowest adiabatic states of the excitonic manifold of interest are known. These three states are reproduced exactly by the procedure while the remaining n − 2 states of the excitonic manifold can be predicted. Explicit conditions are derived permitting to verify whether a given data set is compatible with the effective Frenkel model under study.

Authors:
; ; ;  [1]
  1. Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main (Germany)
Publication Date:
OSTI Identifier:
22308738
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 1; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COUPLINGS; EIGENVALUES; ELECTRONIC STRUCTURE; EXCITED STATES; GROUND STATES; HAMILTONIANS; INTERACTIONS; POLYMERS; POTENTIAL ENERGY

Citation Formats

Binder, Robert, Römer, Sarah, Wahl, Jan, and Burghardt, Irene. An analytic mapping of oligomer potential energy surfaces to an effective Frenkel model. United States: N. p., 2014. Web. doi:10.1063/1.4880415.
Binder, Robert, Römer, Sarah, Wahl, Jan, & Burghardt, Irene. An analytic mapping of oligomer potential energy surfaces to an effective Frenkel model. United States. https://doi.org/10.1063/1.4880415
Binder, Robert, Römer, Sarah, Wahl, Jan, and Burghardt, Irene. 2014. "An analytic mapping of oligomer potential energy surfaces to an effective Frenkel model". United States. https://doi.org/10.1063/1.4880415.
@article{osti_22308738,
title = {An analytic mapping of oligomer potential energy surfaces to an effective Frenkel model},
author = {Binder, Robert and Römer, Sarah and Wahl, Jan and Burghardt, Irene},
abstractNote = {While the use of Frenkel-type models for semiconducting polymer assemblies and related molecular aggregates is well established, the direct parametrization of such models based on electronic structure data is attempted less frequently. In this work, we develop a systematic mapping procedure which is adapted to J-type and H-type homo-aggregate systems. The procedure is based upon the analytic solution of an inverse eigenvalue problem for an effective Frenkel Hamiltonian with nearest-neighbor couplings. Vibronic interactions are included for both site-local and site-correlated modes. For illustration, an application is presented to the excited-state ab initio potential energy surfaces (PESs) of an oligothiophene octamer. The procedure performs a pointwise mapping of the PESs of oligomers of arbitrary chain length n, provided that the electronic ground state and any two of the n lowest adiabatic states of the excitonic manifold of interest are known. These three states are reproduced exactly by the procedure while the remaining n − 2 states of the excitonic manifold can be predicted. Explicit conditions are derived permitting to verify whether a given data set is compatible with the effective Frenkel model under study.},
doi = {10.1063/1.4880415},
url = {https://www.osti.gov/biblio/22308738}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 1,
volume = 141,
place = {United States},
year = {Mon Jul 07 00:00:00 EDT 2014},
month = {Mon Jul 07 00:00:00 EDT 2014}
}