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Ab initio investigation on the structures and spectra of the firefly luciferin

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Abstract

The ground state (S0) geometry of the firefly luciferin (LH2) was optimized by both DFT B3LYP and CASSCF methods. The vertical excitation energies (T v) of three low-lying states (S1, S2, and S3) were calculated by TD-DFT B3LYP//CASSCF method. The S1 geometry was optimized by CASSCF method. Its T v and the transition energy (T e) were calculated by MS-CASPT2//CASSCF method. Both the TD-DFT and MS-CASPT2 calculated S1 state T v values agree with the experimental one. The IPEA shift greatly affects the MS-CASPT2 calculated T v values. Some important excited states of LH2 and oxyluciferin (oxyLH2) are charge-transfer states and have more than one dominant configuration, so for deeply researching the firefly bioluminescence, the multireference calculations are desired.

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  1. College of Chemistry, Beijing Normal University, Beijing, 100875, China

    Liu YaJun & Fang WeiHai

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  1. Liu YaJun
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  2. Fang WeiHai
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Correspondence to Liu YaJun.

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Supported by the National Natural Science Foundation of China (Grant No. 20673012) and the Major State Basic Research Development Programs (Grant No. 2004CB719903)

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Liu, Y., Fang, W. Ab initio investigation on the structures and spectra of the firefly luciferin. Sci. China Ser. B-Chem. 50, 725–730 (2007). https://doi.org/10.1007/s11426-007-0127-4

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  • DOI: https://doi.org/10.1007/s11426-007-0127-4

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