Chem. J. Chinese Universities ›› 2009, Vol. 30 ›› Issue (11(1)): 96.

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PCM-TDDFT Study of the UV-Vis Spectra of Photochromic Spirooxazine and Spiropyran Compound

LIN Bing, CAI Ming , LI Wei*   

  1. College of Chemical Engineering, Wuhan Unviersity of Science and Engineering, Wuhan 430073, China
  • Received:2009-07-28 Online:2009-11-30 Published:2009-11-30
  • Contact: LI Wei. E-mail: liwei_whu@sohu.com
  • Supported by:

    国家自然科学基金(批准号: 20701030)资助.

Abstract:

Photochromic compounds and polymer are new functional materials, which can be widely used in optical information storage, optical conversion devices, optical switches and other fields. In this paper, the electronic absorption spectra of 21 spriooxazine and spiropyran derivatives in close and open-ring states were investigated in the framework of time-dependent density functional theory(TDDFT) with polariable continuum model(PCM) including solvent effect. The B3LYP and PBE0 hybrid functionals together with 6-31+G(d) basis set were selected to calculate the excitation energies of 8—30 lowest-lying singlet excited states. In close-ring states, both PBE0 and B3LYP functional well reproduce the experimental values, and the mean absolute error(MAE) are 0.16 and 0.20 eV, respectively. The mainly absorption bands mainly raise from the ππ* transition from HOMO-1, HOMO to LUMO, LUMO+1. In open-ring states, both PBE0 and B3LYP overestimate the experimental excitation energies by 0.08—0.40 eV, and the MAE is 0.28 and 0.22 eV, respectively. Calculations reveal that the maximum absorption bands mainly result from the transition from HOMO or HOMO-1 to LUMO, and have ππ* characters.

Key words: Spriooxazine; Spiropyran; UV-Vis absorption spectrum; Polarizable continaum model(PCM)-time dependent density furctional theory(TDDFT)

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