Resolution of conformer-specific all-trans-1,6-diphenyl-1,3,5-hexatriene UV absorption spectra

The Journal of Physical Chemistry. a
Andrzej M TurekGovindarajan Krishnamoorthy

Abstract

All-trans-1,6-diphenyl-1,3,5-hexatriene (ttt-DPH) exists in solution as a mixture of s-trans,s-trans and s-cis,s-trans conformers. The latter is higher in energy, and its contribution increases with increasing temperature. ttt-DPH UV absorption spectra broaden with increasing temperature and undergo blue shifts with decreasing polarizability. We describe here the resolution of two spectrothermal matrices of ttt-DPH UV absorption spectra into two conformer-specific components. The first matrix consists of DPH spectra measured in n-dodecane in the 283 to 374 K T range and the second of ttt-DPH absorption spectra measured in the even numbered n-alkanes (n-C(8)-n-C(16)) at temperatures selected to achieve isopolarizability (284-372 K). Principal component analysis (PCA) treatments showed that reasonable two-component systems are attained by compensation for T-induced broadening and shifting in the pure conformer spectra. The self-modeling (SM) method used to resolve the n-C(12) matrix is successfully tested on a simulated matrix closely mimicking ttt-DPH experimental spectra in n-C(12). Compensation for nonlinear effects yields robust two-component matrices from the experimental spectra. Their resolution into pure component spectra...Continue Reading

References

Oct 23, 2003·Analytical Chemistry·Paul H C Eilers
Oct 5, 2006·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Jack Saltiel, Shujun Wang
Jan 1, 1996·Analytical Chemistry·F C SánchezD L Massart

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Citations

Sep 14, 2013·The Journal of Chemical Physics·Takao Itoh
Dec 18, 2013·Biochimica Et Biophysica Acta·Alena StsiapanavaAgnes Rinaldo-Matthis
Mar 7, 2013·The Journal of Physical Chemistry Letters·Christopher RedwoodJack Saltiel

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