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Origin of Spectrum Shifts of Benzophenone–Water Clusters: DFT Study

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Abstract

Structures and electronic excitation energies of the benzophenone–water (Bp–H2O) and benzophenone–methanol (Bp–CH3OH) complexes have been investigated by means of density functional theory calculations. The CAM-B3LYP/6-311++G(d,p) and higher level calculations were carried out for the system. The calculations indicate that free Bp has a nonplanar structure with twist angle of 54.2° for two phenyl rings (referred to as ϕ). In the case of the Bp–H2O system, the twist angle of the phenyl rings and structure of the Bp skeleton were hardly changed by hydration (ϕ = 55.1° for Bp–H2O). However, the excitation energies of Bp were drastically changed by this solvation. The time-dependent density functional calculations show that the n–π* transition (S1 state) is blue-shifted by the solvation, whereas two π–π* transitions (S2 and S3) were red-shifted. The origin of the specific spectral shifts is discussed on the basis of the theoretical results.

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Acknowledgments

The author acknowledges partial support from a Grant-in-Aid for Scientific Research (C) from the Japan Society for the Promotion of Science (JSPS) (Grant Number 24550001). This work was partially supported by a Grant-in-Aid for Scientific Research on Innovation Areas “Evolution of Molecules in Space” (Grant Number 25108004).

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  1. Division of Materials Chemistry, Graduate School of Chemistry, Hokkaido University, Sapporo, 060-8628, Japan

    Tetsuji Iyama, Hiroshi Kawabata & Hiroto Tachikawa

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  1. Tetsuji Iyama
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  2. Hiroshi Kawabata
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Correspondence to Hiroto Tachikawa.

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Iyama, T., Kawabata, H. & Tachikawa, H. Origin of Spectrum Shifts of Benzophenone–Water Clusters: DFT Study. J Solution Chem 43, 1676–1686 (2014). https://doi.org/10.1007/s10953-014-0228-6

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  • DOI: https://doi.org/10.1007/s10953-014-0228-6

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