### Abstract

Orbital energies relevant to the electrochromic conversion were calculated for poly(3,4-propylenedioxythiophene)s (PRs) substituted with different side chains by density functional theory (DFT) calculation to elucidate their color switching and optical memory in electrochromic conversion. The orbital energies of HOMO (E _{HOMO} ), LUMO (E _{LUMO} ), and band gap (E _{g} ) of PRs were calculated for finite-length oligomers up to the hexamer by the DFT calculation and then determined for infinite-length polymers using an extrapolation scheme using the 6-311G(d) basis set. Interestingly the calculated HOMO energies of PRs were dependent on the electronic nature of the side-chains, while experimental energies reflected both electronic and volume of the side chain of PRs. The volume of hexamer was well correlated to the gap between the calculated against experimental E _{HOMO} , with a slope of 0.045 eV/nm ^{3} , indicating that the calculated E _{HOMO} could be accurately correlated to the experimental E _{HOMO} when considering the volume of the side chain. The orbital energies of the PR series were correlated to the EC properties such as color of an electrochromic display (ECD). In particular, ECPs with a low HOMO energy gave a long CM at the bias free. These results provide insights into the EC properties of polymers in terms of their structure–property relationships, tunability of orbital energies by sidechain of PRs, and prediction of optical memory at colored state.

Original language | English |
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Pages (from-to) | 203-215 |

Number of pages | 13 |

Journal | Nonlinear Optics Quantum Optics |

Volume | 50 |

Publication status | Published - 2019 Jan 1 |

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### All Science Journal Classification (ASJC) codes

- Statistical and Nonlinear Physics
- Electronic, Optical and Magnetic Materials
- Computer Science(all)
- Atomic and Molecular Physics, and Optics
- Instrumentation

### Cite this

*Nonlinear Optics Quantum Optics*,

*50*, 203-215.

}

*Nonlinear Optics Quantum Optics*, vol. 50, pp. 203-215.

**Calculation of orbital energies for electrochromic poly(3,4-propylenedioxythiophene)s with different side chains.** / Kanazawa, Kenji; Kim, Younghoon; Shin, Haijin; Kim, Byeonggwan; Han, Minsu; Kim, Eunkyoung.

Research output: Contribution to journal › Article

TY - JOUR

T1 - Calculation of orbital energies for electrochromic poly(3,4-propylenedioxythiophene)s with different side chains

AU - Kanazawa, Kenji

AU - Kim, Younghoon

AU - Shin, Haijin

AU - Kim, Byeonggwan

AU - Han, Minsu

AU - Kim, Eunkyoung

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Orbital energies relevant to the electrochromic conversion were calculated for poly(3,4-propylenedioxythiophene)s (PRs) substituted with different side chains by density functional theory (DFT) calculation to elucidate their color switching and optical memory in electrochromic conversion. The orbital energies of HOMO (E HOMO ), LUMO (E LUMO ), and band gap (E g ) of PRs were calculated for finite-length oligomers up to the hexamer by the DFT calculation and then determined for infinite-length polymers using an extrapolation scheme using the 6-311G(d) basis set. Interestingly the calculated HOMO energies of PRs were dependent on the electronic nature of the side-chains, while experimental energies reflected both electronic and volume of the side chain of PRs. The volume of hexamer was well correlated to the gap between the calculated against experimental E HOMO , with a slope of 0.045 eV/nm 3 , indicating that the calculated E HOMO could be accurately correlated to the experimental E HOMO when considering the volume of the side chain. The orbital energies of the PR series were correlated to the EC properties such as color of an electrochromic display (ECD). In particular, ECPs with a low HOMO energy gave a long CM at the bias free. These results provide insights into the EC properties of polymers in terms of their structure–property relationships, tunability of orbital energies by sidechain of PRs, and prediction of optical memory at colored state.

AB - Orbital energies relevant to the electrochromic conversion were calculated for poly(3,4-propylenedioxythiophene)s (PRs) substituted with different side chains by density functional theory (DFT) calculation to elucidate their color switching and optical memory in electrochromic conversion. The orbital energies of HOMO (E HOMO ), LUMO (E LUMO ), and band gap (E g ) of PRs were calculated for finite-length oligomers up to the hexamer by the DFT calculation and then determined for infinite-length polymers using an extrapolation scheme using the 6-311G(d) basis set. Interestingly the calculated HOMO energies of PRs were dependent on the electronic nature of the side-chains, while experimental energies reflected both electronic and volume of the side chain of PRs. The volume of hexamer was well correlated to the gap between the calculated against experimental E HOMO , with a slope of 0.045 eV/nm 3 , indicating that the calculated E HOMO could be accurately correlated to the experimental E HOMO when considering the volume of the side chain. The orbital energies of the PR series were correlated to the EC properties such as color of an electrochromic display (ECD). In particular, ECPs with a low HOMO energy gave a long CM at the bias free. These results provide insights into the EC properties of polymers in terms of their structure–property relationships, tunability of orbital energies by sidechain of PRs, and prediction of optical memory at colored state.

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M3 - Article

AN - SCOPUS:85061996523

VL - 50

SP - 203

EP - 215

JO - Nonlinear Optics Quantum Optics

JF - Nonlinear Optics Quantum Optics

SN - 1543-0537

ER -