Materials and Device Physics, and Modeling

Theoretical analysis of the solvatochromism of organic dyes differing by the conjugation sequence

[+] Author Affiliations
Sergei Manzhos

National University of Singapore, Department of Mechanical Engineering, Blk EA, #07-08, 9 Engineering Drive 1, Singapore 117576

Makoto Komatsu

University of Tokyo, Research Center for Advanced Science and Technology (RCAST), 4-6-1, Komaba, Meguro-ku, Tokyo 153-8904, Japan

Jotaro Nakazaki

University of Tokyo, Research Center for Advanced Science and Technology (RCAST), 4-6-1, Komaba, Meguro-ku, Tokyo 153-8904, Japan

Hiroshi Segawa

University of Tokyo, Research Center for Advanced Science and Technology (RCAST), 4-6-1, Komaba, Meguro-ku, Tokyo 153-8904, Japan

Koichi Yamashita

University of Tokyo, Department of Chemical System Engineering, School of Engineering, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

J. Photon. Energy. 2(1), 028001 (Aug 03, 2012). doi:10.1117/1.JPE.2.028001
History: Received May 9, 2012; Revised June 29, 2012; Accepted July 10, 2012
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Abstract.  Absorption peak maxima of two organic dyes differing by the position of the methine unit differ by 61 nm in dioxane and by up to 139 nm in polar solvents. It was previously reported that the difference is not reproduced by time-dependent density functional theory (TDDFT) using ab initio or hybrid functionals. TDDFT errors are different between the molecules, leading to a qualitative failure of TDDFT to predict relative energetics of the dyes. We focus on the effect of polar solvents (acetonitrile, DMSO, methanol, and 2-propanol) on the absorption spectrum, specifically, on the different between the two molecules sign of the solvatochromic shift versus dioxane. Using the correction due to Peach et al., the absolute TDDFT errors can be brought within acceptable ranges of 0.2 to 0.3 eV, and the blue shift versus dioxane is reproduced, although both dyes are predicted to exhibit positive solvatochromism. The inclusion of explicit solvent molecules did not appreciably change either TDDFT energies or the correction term. These results show that in dye design by changing the conjugation order, computational errors are expected to be more important than in the case of an extension of the size of conjugation, especially when polar solvents are used.

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© 2012 Society of Photo-Optical Instrumentation Engineers

Citation

Sergei Manzhos ; Makoto Komatsu ; Jotaro Nakazaki ; Hiroshi Segawa and Koichi Yamashita
"Theoretical analysis of the solvatochromism of organic dyes differing by the conjugation sequence", J. Photon. Energy. 2(1), 028001 (Aug 03, 2012). ; http://dx.doi.org/10.1117/1.JPE.2.028001


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