Fermi resonance structure and femtosecond quantum dynamics of a chiral molecule from the analysis of vibrational overtone spectra of CHBrClF

The rovibrational spectra of bromochlorofluoromethane (CHBrClF) were measured at intermediate (0.1 cm -1 ) and high resolution (0.001 cm -1 ) between the far infrared (20 cm -1 ) and the visible range of the spectrum (14 000 cm -1 ) by interferometric Fourier transform techniques and diode laser techniques in stationary samples and supersonic jets. All fundamentals and numerous combinations and overtone transitions could be assigned and their band positions and integrated strengths were determined. A quantitative interpretation of the complex multiple resonance structure of the CH chromophore spectra (about 50 assigned bands) is given in terms of an effective anharmonic CH-stretching-bending Hamiltonian and in terms of vibrational variational calculations on a 3-dimensional grid using ab initio (MP2 and B3LYP) and empirically adjusted potential hypersurfaces for the CH chromophore normal coordinate subspace. The systematic analysis of anharmonic resonances of the alkyl CH chromophore in symmetric top (C 3v ) and asymmetric top (C s ) molecules is herewith extended to chiral molecules. We provide a detailed analysis of the chiral C s symmetry breaking coupling in the effective Hamiltonian (coupling constant |k' sab | ≃ (20±10) cm -1 ) and in the potential (C sab and further terms) and their relationship. The implications for the femtosecond intramolecular dynamics for CHBrCIF are discussed in terms of quantum dynamical results for time-dependent populations, survival probabilities, wavepackets and also time-dependent symmetries and their violations (formal a' and a species for vibrational C s and l quantum number for vibrational C∞ v symmetry). We have also developed an improved synthesis of CHBrCIF, which is suitable for the preparation of large quantities (several mol) of the pure (racemic) compound, and have demonstrated enantiomer separation by gas chromatography.

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