Insight on relationship between crystallinity and band gap energies of polyhydroxyalkanoates polymers

• Published in: Materials today communications Vol. 39; p. 108886
• Main Authors: Ghorabe, Fares D.E., Novikov, Alexander S., Nesterov, Pavel V., Galina, A. Ryltseva, Dudaev, Alexey E., Shishatskaya, Ekaterina I., Skorb, Ekaterina V.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01-06-2024
• Subjects: Band gap energy; Biodegradable polymers; Crystallinity; Density functional theory (DFT); Electronic properties; Polyhydroxyalkanoates (PHAs); Band gap energy; Electronic properties; Crystallinity; Density functional theory (DFT); Biodegradable polymers; Polyhydroxyalkanoates (PHAs)
• ISSN: 2352-4928; 2352-4928
• DOI: 10.1016/j.mtcomm.2024.108886

This study explores the electronic properties of polyhydroxyalkanoates (PHAs), a class of biodegradable polymers. The focus lies in examining the relationship between crystallinity and band gap energies in PHAs. A notable discovery is the identification of a band gap plateau, suggesting a threshold in electronic properties with increasing polymer chain length. DFT calculations were employed to model the complexities of PHA polymers, with the conductor-like polarizable continuum model (CPCM) offering insights into solvent effects. The results demonstrate a strong negative correlation between crystallinity and band gap in both vacuum and CPCM environments. This study underscores the significance of structural order in shaping the electronic properties of PHAs, paving the way for the development of sustainable polymeric materials for various applications.
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•DFT calculations performed on 10-monomer oligomers in vacuum and CPCM-simulated solvent.•Examination of monomer ratio variations in oligomers, revealing compositional effects on HOMO and LUMO energies.•Solvent environment (CPCM) generally increases both HOMO and LUMO energies, with a stronger impact on LUMO, indicating solvent-induced stabilization.•Higher proportions of the second monomer type in oligomers lead to a notable band gap energy stabilization (plateau), highlighting the importance of monomer ratio.•Demonstrated potential for tailored electronic properties in oligomeric materials by controlling monomer composition, applicable in electronic and optoelectronic devices.