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Volumn 102, Issue 21, 1998, Pages 4240-4246

Investigation of the relationship between dipolar properties and cis-trans configuration in retinal polyenes: A comparative study using stark spectroscopy and semiempirical calculations

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EID: 11644318578     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp980562t     Document Type: Review
Times cited : (58)

References (60)
  • 1
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    • Wald, G. Nature 1968, 219, 800-807.
    • (1968) Nature , vol.219 , pp. 800-807
    • Wald, G.1
  • 8
    • 11644271869 scopus 로고
    • Ph.D. Thesis, Univ. of CA, Riverside
    • Hubbard, L. M. Ph.D. Thesis, Univ. of CA, Riverside, 1980.
    • (1980)
    • Hubbard, L.M.1
  • 24
    • 11644300373 scopus 로고    scopus 로고
    • note
    • m.
  • 26
    • 0001269334 scopus 로고
    • Lim, E. C., Ed.; Academic Press: New York
    • Liptay, W. In Excited States; Lim, E. C., Ed.; Academic Press: New York, 1974; pp 129-229.
    • (1974) Excited States , pp. 129-229
    • Liptay, W.1
  • 28
    • 0001718556 scopus 로고
    • Mathies, R.; Stryer, L. Proc. Natl. Acad. Sci. U.S.A. 1976, 73, 2169-2173. In dioxane solutions, they measured |Δμ| = 15.6 ± 1.0 D and |m·Δμ| = 14.7 ± 2.1 D for ATR, and |Δμ| = 9.9 ± 0.5 D and |m·Δμ| = 10.2 ± 0.9 D for ATR-SB.
    • (1976) Proc. Natl. Acad. Sci. U.S.A. , vol.73 , pp. 2169-2173
    • Mathies, R.1    Stryer, L.2
  • 43
    • 11644303948 scopus 로고    scopus 로고
    • note
    • For ATR (Table 1), our |Δμ| are 30% to 40% lower and our Δα are within the range of values previously reported by other groups utilizing electroabsorption (see refs 27-29). However, using a combination of dielectric constant data and solvatochromic behavior, Corsetti and Kohler (ref 60) estimated |Δμ| to be 5.7 D, which is smaller than our measured value. In the retinal SB isomers (Table 2), |Δμ| are larger than those of the aldehydes (Table 1) in both cis isomers and are within 30% of reported values (ref 28) for ATR-SB (|Δμ| = 9.9 D, |m·Δμ = 10.2 D).
  • 48
    • 85088283158 scopus 로고    scopus 로고
    • note
    • g. One might expect that a term of this type would be necessary to adequately model solvent effects on Δα in polar systems. We are currently investigating calculations of this type.
  • 57
    • 11644325133 scopus 로고    scopus 로고
    • note
    • Assuming all of the measured Δα arises from orientation (nuclear) polarization allows us to estimate the extent of ATR reorientation to be ±10-20°. This amounts to a total of 20-40°, which is very large considering the size of the retinal. It is also possible that solvent molecules trapped in the polymer matrix may be reorienting.


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