Evaluation of electronic polarization energy in oligoacene molecular crystals using the solvated supermolecular approach

View/ Open
Author(s)
Xu, Tao
Wang, Wenliang
Yin, Shiwei
Wang, Yun
Griffith University Author(s)
Year published
2017
Metadata
Show full item recordAbstract
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 ...
View more >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.
View less >
View more >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.
View less >
Journal Title
Physical Chemistry Chemical Physics
Volume
19
Issue
22
Copyright Statement
© 2017 Royal Society of Chemistry. This is the author-manuscript version of this paper. Reproduced in accordance with the copyright policy of the publisher. Please refer to the journal website for access to the definitive, published version.
Subject
Electroanalytical Chemistry
Physical Sciences
Chemical Sciences
Engineering