Effects of internal electron-withdrawing moieties in d−a−π−a organic sensitizers on photophysical properties for DSSCs: A computational study

Chih Chiang Chiu, Yung Ching Sheng, Wei Jen Lin, Ratna Juwita, Chun Jui Tan, Hui Hsu Gavin Tsai

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

D−A−π−A dyes differ from the traditional D−π−A framework having several merits in dye-sensitized solar cell (DSSC) applications. With regard to D−π−A dyes, D−A−π−A dyes red-shift absorption spectra and show particular photostability. Nevertheless, the effects of internal acceptor on the charge transfer (CT) probability are unclear. We employed density functional theory (DFT), time-dependent DFT (TD-DFT), and TD-DFT molecular dynamics (MD) simulations to investigate the effects of internal acceptor on the photophysical properties of D−A−π−A dyes on DSSCs. Our calculations show the absorption bands of D−A−π−A dyes with strong electron-withdrawing internal acceptors exhibiting significant characteristics of dual CT; the excited electron density is transferred to the internal and terminal acceptors simultaneously. Particularly, the internal acceptor traps a significant amount of electron density upon photoexcitation. The TD-DFT MD simulations at 300 K show that only a small amount of excited electron density is pushing and pulling between the internal acceptor and terminal acceptor moieties; the thermal energy is not high enough to drive the electron density from the internal acceptor to the terminal acceptor. Our study reveals the nature of CT bands of D−A−π−A dyes providing a theoretical basis for further rational engineering.

Original languageEnglish
Pages (from-to)433-445
Number of pages13
JournalACS Omega
Volume3
Issue number1
DOIs
StatePublished - 31 Jan 2018

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