Abstract
Isotropic and anistropic Raman band shape analyses of the ν2(a1) mode (the Cl–P–Cl bending) of phosphorous trichloride are reported for the pure liquid and carbon tetrachloride solutions. The experimental values are compared with those calculated for the free gas molecule reorientation and the angular velocity correlation times and with those obtained from Stokes–Einstein theory. It is shown that the PCl3 molecule tumbling about the axes perpendicular to the C3 axis in the pure liquid proceeds by small-step Brownian diffusion and is associated with an Arrhenius activation energy of 7.1 kJ mol−1, in good agreement with reported NMR data. The vibrational linewidth of the ν2(a1) mode does not depend strongly on temperature and concentration. Intramolecular vibrational energy exchange with nearby states is assumed as the main fraction of the vibrational relaxation of this mode.
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