UV-visible absorption and resonance Raman (RR) spectra of liquid bromine are presented and rigorously interpreted. The RR spectra, which show an anharmonic vibrational progression of up to 30 overtones, define the ground state potential in the range 2.05 Aor=25 to >or=2.4 ps between v=1 and v=25. Remarkably, the RR line shapes are skewed toward the red, indicating upchirp in frequencies that develop over a period of 400 fs. Evidently, the molecular vibrations adiabatically follow the solvent cage, which is impulsively driven into expansion during the approximately 20 fs evolution on the electronically excited state. Liquid bromine retains coherence in ordered sluggish local cages with quadrupolar interactions-dynamics akin to molecules isolated in structured cryogenic rare gas solids.

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http://dx.doi.org/10.1063/1.3291610DOI Listing

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