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Computation 2013, 1(1), 1-15; doi:10.3390/computation1010001
Article

Effect of Isotopic Substitution on Elementary Processes in Dye-Sensitized Solar Cells: Deuterated Amino-Phenyl Acid Dyes on TiO2

1,* , 2,†
 and 3,†
Received: 23 January 2013; in revised form: 4 February 2013 / Accepted: 1 March 2013 / Published: 11 March 2013
(This article belongs to the Special Issue Feature Papers)
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Abstract: We present the first computational study of the effects of isotopic substitution on the operation of dye-sensitized solar cells. Ab initio molecular dynamics is used to study the effect of deuteration on light absorption, dye adsorption dynamics, the averaged over vibrations driving force to injection (∆Gi) and regeneration (∆Gr), as well as on promotion of electron back-donation in dyes NK1 (2E,4E-2-cyano-5-(4-dimethylaminophenyl)penta-2,4-dienoic acid) and NK7 (2E,4E-2-cyano-5-(4-diphenylaminophenyl)penta-2,4-dienoic acid) adsorbed in monodentate molecular and bidentate bridging dissociative configurations on the anatase (101) surface of TiO2. Deuteration causes a red shift of the absorption spectrum of the dye/TiO2 complex by about 5% (dozens of nm), which can noticeably affect the overlap with the solar spectrum in real cells. The dynamics effect on the driving force to injection and recombination (the difference between the averaged <∆Gi,r> and ∆Gi,requil at the equilibrium configuration) is strong, yet there is surprisingly little isotopic effect: the average driving force to injection <∆Gi> and to regeneration <∆Gr> changes by only about 10 meV upon deuteration. The nuclear dynamics enhance recombination to the dye ground state due to the approach of the electron-donating group to TiO2, yet this effect is similar for deuterated and non-deuterated dyes. We conclude that the nuclear dynamics of the C-H(D) bonds, mostly affected by deuteration, might not be important for the operation of photoelectrochemical cells based on organic dyes. As the expectation value of the ground state energy is higher than its optimum geometry value (by up to 0.1 eV in the present case), nuclear motions will affect dye regeneration by recently proposed redox shuttle-dye combinations operating at low driving forces.
Keywords: dye-sensitized solar cells; molecular dynamics; deuteration; isotopic substitution; electron injection; recombination; dye regeneration dye-sensitized solar cells; molecular dynamics; deuteration; isotopic substitution; electron injection; recombination; dye regeneration
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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MDPI and ACS Style

Manzhos, S.; Segawa, H.; Yamashita, K. Effect of Isotopic Substitution on Elementary Processes in Dye-Sensitized Solar Cells: Deuterated Amino-Phenyl Acid Dyes on TiO2. Computation 2013, 1, 1-15.

AMA Style

Manzhos S, Segawa H, Yamashita K. Effect of Isotopic Substitution on Elementary Processes in Dye-Sensitized Solar Cells: Deuterated Amino-Phenyl Acid Dyes on TiO2. Computation. 2013; 1(1):1-15.

Chicago/Turabian Style

Manzhos, Sergei; Segawa, Hiroshi; Yamashita, Koichi. 2013. "Effect of Isotopic Substitution on Elementary Processes in Dye-Sensitized Solar Cells: Deuterated Amino-Phenyl Acid Dyes on TiO2." Computation 1, no. 1: 1-15.

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