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Title: Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study

Abstract

We establish a reliable quantum-mechanical approach to evaluate the vibrational properties of donor-acceptor molecular crystals. The anthracene-PMDA (PMDA = pyromellitic dianhydride) crystal, where anthracene acts as the electron donor and PMDA as the electron acceptor, is taken as a representative system for which experimental non-resonance Raman spectra are also reported. We first investigate the impact that the amount of nonlocal Hartree-Fock exchange (HFE) included in a hybrid density functional has on the geometry, normal vibrational modes, electronic coupling, and electron-vibrational (phonon) couplings. The comparison between experimental and theoretical Raman spectra indicates that the results based on the αPBE functional with 25%-35% HFE are in better agreement with the experimental results compared to those obtained with the pure PBE functional. Then, taking αPBE with 25% HFE, we assign the vibrational modes and examine their contributions to the relaxation energy related to the nonlocal electron-vibration interactions. The results show that the largest contribution (about 90%) is due to electron interactions with low-frequency vibrational modes. The relaxation energy in anthracene-PMDA is found to be about five times smaller than the electronic coupling.

Authors:
; ; ;  [1]; ;  [2]
  1. Department of Physics and Astronomy, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3255 (United States)
  2. Department of Physics, Wake Forest University, Winston-Salem, North Carolina 27109-7507 (United States)
Publication Date:
OSTI Identifier:
22493324
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 22; Other Information: (c) 2015 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; ANHYDRIDES; ANTHRACENE; BINDING ENERGY; COMPARATIVE EVALUATIONS; DENSITY FUNCTIONAL METHOD; ELECTRONS; HARTREE-FOCK METHOD; HYBRIDIZATION; MOLECULAR CRYSTALS; PHONONS; QUANTUM MECHANICS; RAMAN SPECTRA; RELAXATION; VALENCE

Citation Formats

Fonari, A., Corbin, N. S., Coropceanu, V., E-mail: jean-luc.bredas@kaust.edu.sa, E-mail: coropceanu@gatech.edu, Vermeulen, D., McNeil, L. E., Goetz, K. P., Jurchescu, O. D., Bredas, J. L., E-mail: jean-luc.bredas@kaust.edu.sa, E-mail: coropceanu@gatech.edu, and Solar and Photovoltaics Engineering Research Center, Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900. Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study. United States: N. p., 2015. Web. doi:10.1063/1.4936965.
Fonari, A., Corbin, N. S., Coropceanu, V., E-mail: jean-luc.bredas@kaust.edu.sa, E-mail: coropceanu@gatech.edu, Vermeulen, D., McNeil, L. E., Goetz, K. P., Jurchescu, O. D., Bredas, J. L., E-mail: jean-luc.bredas@kaust.edu.sa, E-mail: coropceanu@gatech.edu, & Solar and Photovoltaics Engineering Research Center, Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900. Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study. United States. doi:10.1063/1.4936965.
Fonari, A., Corbin, N. S., Coropceanu, V., E-mail: jean-luc.bredas@kaust.edu.sa, E-mail: coropceanu@gatech.edu, Vermeulen, D., McNeil, L. E., Goetz, K. P., Jurchescu, O. D., Bredas, J. L., E-mail: jean-luc.bredas@kaust.edu.sa, E-mail: coropceanu@gatech.edu, and Solar and Photovoltaics Engineering Research Center, Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900. Mon . "Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study". United States. doi:10.1063/1.4936965.
@article{osti_22493324,
title = {Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study},
author = {Fonari, A. and Corbin, N. S. and Coropceanu, V., E-mail: jean-luc.bredas@kaust.edu.sa, E-mail: coropceanu@gatech.edu and Vermeulen, D. and McNeil, L. E. and Goetz, K. P. and Jurchescu, O. D. and Bredas, J. L., E-mail: jean-luc.bredas@kaust.edu.sa, E-mail: coropceanu@gatech.edu and Solar and Photovoltaics Engineering Research Center, Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900},
abstractNote = {We establish a reliable quantum-mechanical approach to evaluate the vibrational properties of donor-acceptor molecular crystals. The anthracene-PMDA (PMDA = pyromellitic dianhydride) crystal, where anthracene acts as the electron donor and PMDA as the electron acceptor, is taken as a representative system for which experimental non-resonance Raman spectra are also reported. We first investigate the impact that the amount of nonlocal Hartree-Fock exchange (HFE) included in a hybrid density functional has on the geometry, normal vibrational modes, electronic coupling, and electron-vibrational (phonon) couplings. The comparison between experimental and theoretical Raman spectra indicates that the results based on the αPBE functional with 25%-35% HFE are in better agreement with the experimental results compared to those obtained with the pure PBE functional. Then, taking αPBE with 25% HFE, we assign the vibrational modes and examine their contributions to the relaxation energy related to the nonlocal electron-vibration interactions. The results show that the largest contribution (about 90%) is due to electron interactions with low-frequency vibrational modes. The relaxation energy in anthracene-PMDA is found to be about five times smaller than the electronic coupling.},
doi = {10.1063/1.4936965},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 22,
volume = 143,
place = {United States},
year = {2015},
month = {12}
}