Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study
Journal Article
·
· Journal of Chemical Physics
- Department of Physics and Astronomy, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3255 (United States)
- Department of Physics, Wake Forest University, Winston-Salem, North Carolina 27109-7507 (United States)
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.
- OSTI ID:
- 22493324
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 143; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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