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Author Fonari, A. ♦ Corbin, N. S. ♦ Coropceanu, V. ♦ Vermeulen, D. ♦ McNeil, L. E. ♦ Goetz, K. P. ♦ Jurchescu, O. D. ♦ Bredas, J. L. ♦ Solar
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword 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
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.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2015-12-14
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 143
Issue Number 22


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