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Direct determination of molar absorption coefficients of several molecules in the lowest excited singlet states

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Abstract

Molar absorption coefficient of the lowest excited state is an indispensable information for the quantitative investigation of photochemical reactions by means of transient absorption spectroscopy. In the present work, we quantitatively estimated the molar absorption coefficients of the S1 state of the solute in three solution systems, Rhodamine B in ethanol, ZnTPP in DMF and N,N’-bis(2,6-diisopropylphenyl)terrylene-3,4,11,12-tetracarboxydiimide (TDI) in chloroform, by perfectly bleaching the ground state molecules using the picosecond 532-nm laser pulse with a large number of photons. These solution systems were selected because no obvious photodegradation was detected in the present range of the excitation intensity. The molar absorption coefficient obtained by this method was verified by the numerical analysis of the excitation intensity dependence of the transient absorbance by taking into account the inner filter effect (absorption of the excitation light by the S1 state produced by the leading part of the pump pulse) and the decrease of the ground state molecules by the pump process (depletion). In addition, these molar absorption coefficients were confirmed by the comparison of relations between the excitation intensity and the transient absorbance of the S1 state under the condition where the fraction of the excited solute is ≪ 10% by the femtosecond pulsed laser excitation. From these results, the error of the molar absorption coefficients was estimated to be < 5%. These values can be used as reference ones for the estimation of molar absorption coefficients of other systems leading to the quantitative elucidation of the photochemical reactions detected by the transient absorption spectroscopy.

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Acknowledgements

The authors appreciate Mr. Yuto Masaoka and Mr. Tsubasa Hidaka at Ritsumeilkan University for their assistance in the fs experiments.

Funding

This work was supported partly by JSPS KAKENHI Grant Numbers JP26107002 and 21H01889 to HM, No. 19J13917 for JSPS Research Fellow to M.K and the Research Foundation for Opto-Science and Technology to HS.

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Authors and Affiliations

  1. Division of Frontier Materials Science and Center for Advanced Interdisciplinary Research, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan

    Masafumi Koga, Hikaru Sotome, Naoki Ide, Syoji Ito & Hiroshi Miyasaka

  2. Department of Applied Chemistry, College of Life Sciences, Ritsumeikan University, 1-1-1 Noji-Higashi, Kusatsu, Shiga, 525-8577, Japan

    Yutaka Nagasawa

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  1. Masafumi Koga
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  2. Hikaru Sotome
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  4. Syoji Ito
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  6. Hiroshi Miyasaka
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Corresponding author

Correspondence to Hiroshi Miyasaka.

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Supplementary Information

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43630_2021_104_MOESM1_ESM.txt

Transient absorption spectra of RhB in ethanol, ZnTPP in DMF and TDI in chloroform are available as files, RhB_ethanol_S1.txt, ZnTPP_DMF_S1.txt, and TDI_CHCL3_S1.txt. These spectra are provided as difference absorption between the S1 and S0 state including the stimulated emission, as were shown Figures 3, 6, and 9. (TXT 14 kb)

Supplementary file2 (TXT 15 kb)

Supplementary file3 (TXT 17 kb)

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Koga, M., Sotome, H., Ide, N. et al. Direct determination of molar absorption coefficients of several molecules in the lowest excited singlet states. Photochem Photobiol Sci 20, 1287–1297 (2021). https://doi.org/10.1007/s43630-021-00104-z

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  • DOI: https://doi.org/10.1007/s43630-021-00104-z

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