Conformational Isomerization of bis-(4-HYDROXYPHENYL)METHANE in a Supersonic Jet Expansion. Part II: Internal Mixing and Low Barrier Potential Energy Surface in the S_{1} State.

Details Conformational Isomerization of bis-(4-HYDROXYPHENYL)METHANE in a Supersonic Jet Expansion. Part II: Internal Mixing and Low Barrier Potential Energy Surface in the S_{1} State. Conformational Isomerization of bis-(4-HYDROXYPHENYL)METHANE in a Supersonic Jet Expansion. Part II: Internal Mixing and Low Barrier Potential Energy Surface in the S_{1} State.

Jun 2009

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2009mss..confemf06m&link_type=abstract

"International Symposium On Molecular Spectroscopy, 64th Meeting, Held 22-26 June, 2009 at Ohio State University. http://molspec

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Dynamics

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The close proximity of two identical ultraviolet chromophores render bis-(4-hydroxyphenyl)methane (B4HPM) an interesting case for the study of the dependence of excitonic coupling on the distortion along low-frequency large-amplitude vibrational coordinates, in particular the phenol ring torsional coordinates present in B4HPM. We have studied the fluorescence excitation spectrum, the UV-UV holeburning spectra and several single vibronic level fluorescence spectra of the tilde{A}^{1}B(S_{1}) ← tilde{X}^{1}A(S_{0}) and the tilde{B}^{1}A(S_{2}) ← tilde{X}^{1}A(S_{0}) transition of all three conformers of B4HPM in a supersonic jet. Excitonic splitting between the two chromophores shifts the second excited state S_{2} ← S_{0} by merely 132 cm^{-1} from the S_{1} ← S_{0} origin in both symmetric conformers. The analysis of the dispersed fluorescence spectra of the S_{2} origins reveals that these levels are internally mixed with nearby S_{1} vibronic levels, providing a fingerprint of the levels involved in the mixing. The dispersed fluorescence spectra of several low-energy S_{1} ← S_{0} vibronic transitions of a specific conformer were taken under systematic variation of the collision frequency in the region where supersonic jet and laser pulse train intersect. These spectra reveal fluorescence contributions from the other two conformers, thus indicating the presence of low-energy conformational barriers (˜ 40-80 cm^{-1}) in the S_{1} state of B4HPM.

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