Abstract
The recent improvements in metal-free organic dye-sensitized solar cells (DSSCs) have been attributed to the ability to tune the optical and electronic properties through various structural modifications. Within the donor-π-conjugated spacer-acceptor (D-π-A) architecture, the electron-donating and accepting strengths have been proven to be major control variables for increasing the energy conversion efficiency. In the present study, a series of metal-free organic D-π-A dyes for DSSCs were designed and investigated. In particular, the electron donating strength was modulated by adding electron donating groups to the donor side. The HOMO energy increased with a gradual increase in donor strength which was verified by an investigation of the bond distances between the nitrogen and carbon atom of phenyl ring connected with π-conjugated spacer. The net electron transfer from the donor to acceptor, calculated from natural bond orbital (NBO) analysis, also showed quantitative correlation with the bond distances. Finally, the absorption peak shifted to a longer wavelength with the increase of donor strength as well as π-conjugated spacer. Detailed analysis of the results supported that all properties investigated has a strong correlation with the bond distance between the nitrogen and the carbon atom in the phenyl ring attached to the π-conjugated spacer. Based on this apparent correlation, this bond distance from ground-state DFT calculations may be used as a descriptor for the high throughput screening of DSSC dyes instead of using computationally expensive TDDFT calculations.
| Original language | English |
|---|---|
| Pages (from-to) | 30-37 |
| Number of pages | 8 |
| Journal | Computational and Theoretical Chemistry |
| Volume | 1081 |
| DOIs | |
| Publication status | Published - 2016 Apr 1 |
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Keywords
- Density functional theory
- Donating ability
- Metal free DSSCs
- π-spacer
ASJC Scopus subject areas
- Biochemistry
- Condensed Matter Physics
- Physical and Theoretical Chemistry
Cite this
DFT computational investigation of tuning the electron donating ability in metal-free organic dyes featuring a thienylethynyl spacer for dye sensitized solar cells. / Seo, Dongkyun; Park, Kwang Won; Kim, Jiyoon; Hong, Jongin; Kwak, Kyungwon.
In: Computational and Theoretical Chemistry, Vol. 1081, 01.04.2016, p. 30-37.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - DFT computational investigation of tuning the electron donating ability in metal-free organic dyes featuring a thienylethynyl spacer for dye sensitized solar cells
AU - Seo, Dongkyun
AU - Park, Kwang Won
AU - Kim, Jiyoon
AU - Hong, Jongin
AU - Kwak, Kyungwon
PY - 2016/4/1
Y1 - 2016/4/1
N2 - The recent improvements in metal-free organic dye-sensitized solar cells (DSSCs) have been attributed to the ability to tune the optical and electronic properties through various structural modifications. Within the donor-π-conjugated spacer-acceptor (D-π-A) architecture, the electron-donating and accepting strengths have been proven to be major control variables for increasing the energy conversion efficiency. In the present study, a series of metal-free organic D-π-A dyes for DSSCs were designed and investigated. In particular, the electron donating strength was modulated by adding electron donating groups to the donor side. The HOMO energy increased with a gradual increase in donor strength which was verified by an investigation of the bond distances between the nitrogen and carbon atom of phenyl ring connected with π-conjugated spacer. The net electron transfer from the donor to acceptor, calculated from natural bond orbital (NBO) analysis, also showed quantitative correlation with the bond distances. Finally, the absorption peak shifted to a longer wavelength with the increase of donor strength as well as π-conjugated spacer. Detailed analysis of the results supported that all properties investigated has a strong correlation with the bond distance between the nitrogen and the carbon atom in the phenyl ring attached to the π-conjugated spacer. Based on this apparent correlation, this bond distance from ground-state DFT calculations may be used as a descriptor for the high throughput screening of DSSC dyes instead of using computationally expensive TDDFT calculations.
AB - The recent improvements in metal-free organic dye-sensitized solar cells (DSSCs) have been attributed to the ability to tune the optical and electronic properties through various structural modifications. Within the donor-π-conjugated spacer-acceptor (D-π-A) architecture, the electron-donating and accepting strengths have been proven to be major control variables for increasing the energy conversion efficiency. In the present study, a series of metal-free organic D-π-A dyes for DSSCs were designed and investigated. In particular, the electron donating strength was modulated by adding electron donating groups to the donor side. The HOMO energy increased with a gradual increase in donor strength which was verified by an investigation of the bond distances between the nitrogen and carbon atom of phenyl ring connected with π-conjugated spacer. The net electron transfer from the donor to acceptor, calculated from natural bond orbital (NBO) analysis, also showed quantitative correlation with the bond distances. Finally, the absorption peak shifted to a longer wavelength with the increase of donor strength as well as π-conjugated spacer. Detailed analysis of the results supported that all properties investigated has a strong correlation with the bond distance between the nitrogen and the carbon atom in the phenyl ring attached to the π-conjugated spacer. Based on this apparent correlation, this bond distance from ground-state DFT calculations may be used as a descriptor for the high throughput screening of DSSC dyes instead of using computationally expensive TDDFT calculations.
KW - Density functional theory
KW - Donating ability
KW - Metal free DSSCs
KW - π-spacer
UR - http://www.scopus.com/inward/record.url?scp=84958971865&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84958971865&partnerID=8YFLogxK
U2 - 10.1016/j.comptc.2016.02.009
DO - 10.1016/j.comptc.2016.02.009
M3 - Article
AN - SCOPUS:84958971865
VL - 1081
SP - 30
EP - 37
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
SN - 2210-271X
ER -