Density Functional Theoretical Analysis of the Molecular Structural Effects on Raman Spectra of β-Carotene and Lycopene

Authors

  • Weilong Liu,

    Corresponding author
    1. School of Materials Science and Engineering, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China
    2. Department of Physics, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China
    • School of Materials Science and Engineering, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China, Tel.: 0086-0451-86418430; Fax: 0086-0451-86418440
    Search for more papers by this author
  • Zhigang Wang,

    1. Institute of Atomic and Molecular Physics, Jilin University, Changchun, Jilin 130012, China
    Search for more papers by this author
  • Zhiren Zheng,

    Corresponding author
    1. Department of Physics, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China
    • Department of Physics, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China
    Search for more papers by this author
  • Lilin Jiang,

    1. Department of Physics, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China
    2. Department of Physics and Electronics Information Engineering, Hezhou University, Hezhou, Guangxi 542800, China
    Search for more papers by this author
  • Yanqiang Yang,

    1. Department of Physics, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China
    Search for more papers by this author
  • Liancheng Zhao,

    1. School of Materials Science and Engineering, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China
    Search for more papers by this author
  • Wenhui Su

    1. Department of Physics, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China
    Search for more papers by this author

Abstract

The molecular structural and Raman spectroscopic characteristics of β-carotene and lycopene are investigated by density functional calculations. The effects of molecular structure and solvent environment on the Raman spectra are analyzed by comparing the calculated and measured results. It is found that the B3LYP/6-31G(d) method can predict the reasonable result for β-carotene, but the ν1 Raman activities of lycopene overflow at all the used theoretical methods because of the longer conjugation length. The calculated results indicate that the rotation of β-rings in β-carotene impedes the delocalization of π-electrons, shortens the effective conjugation length, and results in higher frequency and lower activity of the ν1 mode in β-carotene than lycopene. The measured ν1 bands of β-carotene and lycopene shift respectively to higher and lower frequencies in solution compared with that in crystals since the crystal packing forces can lead to different conformational variations in the carotenoids molecules. The polarized continuum model theoretical analysis suggests that solvent has slight (significant) effects on the Raman frequencies (intensities) of both carotenoids.

Ancillary