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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Evaluation of electronic polarization energy in oligoacene molecular crystals using the solvated supermolecular
Tao Xu1, Wenliang Wang, Shiwei Yin
1Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an city, 710062, China. yin_sw@snnu.edu.cn.
Abstract:
The solvated supermolecular approach, i.e., block-localized wave function coupled with polarizable continuum model (BLW/PCM), was proposed to calculate molecular ionization potential (IP), electron affinity (EA) in the solid phase, and related electronic polarization. Via the calculations of a solvated supermolecule (5M), including four closest molecules, BLW/PCM overcomes the limitation in the calculation for the monomer PCM, that is, nearly same electronic polarization for cation (P+) and anion (P-). The solvated supermolecular approach successfully described asymmetric behaviors of P+ and P- for oligoacene crystals. In addition, we also compared two charge-localized methods, i.e., BLW and constrained density functional theory (CDFT), to calculate the molecular IP and EA in supermolecules with/without PCM. Our results demonstrate that both the BLW and CDFT correctly estimate the EA and IP values in the gas phase cluster, whereas CDFT/PCM fails to evaluate the P- value of the bulk system.
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