Abstract
In this work an analysis of the highly vibrationally excited states of thiophosgene (SCCl2) is made in order to gain insights into some of the experimental observations and spectral features. The states analysed here lie in a spectrally complex region where strong mode mixings are expected due to the overlap of several strong anharmonic Fermi resonances. Two recent techniques, a semiclassical angle space representation of the eigenstates and the parametric variation of the eigenvalues (level-velocities) are used to identify eigenstate sequences exhibiting common localization characteristics. Preliminary results on the influence of highly excited out-of-plane bending modes on the nature of the eigenstates suggest a possible bifurcation in the system.
Dynamical assignment of highly vibrationally excited states of thiophosgene is made using two recent techniques based on classical-quantum correspondence. The analysis give insights into eigenstate sequences and predicts possible bifurcations at energies far above the ground state.
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#Dedicated to Prof. N Sathyamurthy on his 60th birthday
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KESHAVAMURTHY, S. On the nature of highly vibrationally excited states of thiophosgene# . J Chem Sci 124, 291–300 (2012). https://doi.org/10.1007/s12039-012-0228-2
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DOI: https://doi.org/10.1007/s12039-012-0228-2