ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
From a combined theoretical and experimental study of 1,2,4,5-tetrachlorobenzene (TCB) we conclude that this crystal shows many interesting effects. In agreement with earlier optical measurements, which probe the complete vibron band structure of TCB, we calculate that several of the vibron modes have the dispersion of a one-dimensional crystal with stacks of molecules along the a axis. The inclusion of fractional atomic charges in the atom–atom potential used in the calculations is absolutely necessary to obtain the correct vibron bandwidths. Also the sign of the vibrational coupling matrix elements, which is given correctly by the calculations, is determined by these charges. For other properties, such as the crystal stability, the phonon frequencies, the site splitting in the vibron bands, and also the dispersion of the lower frequency vibrations, the interactions between the "one-dimensional'' stacks are essential, however. The calculations predict further, in qualitative agreement with the Raman spectra, that the splitting between the pairs of inequivalent vibron bands in α-TCB (the site splitting) is significantly larger than the factor group splitting in β-TCB. Finally we have found that, for those vibrations where the conditions are shown by the calculations to be favorable, the 35Cl/37Cl isotope effects are clearly visible in the Raman spectra.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.454835
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