Abstract

The molecular crystal of benzil, [C 6 H 5 CO] 2, is known to undergo a phase transition at T c = 84 K. The phase transition is from a high temperature trigonal phase with space group D 4 3 (P3 121) to a low temperature monoclinic phase with space group C 3 2 (C 2). This paper reports a study of the exciton structure of the infrared bands of benzil as a function of temperature in the vicinity of T c = 84 K. The benzil molecule belongs to the C 2 molecular point group. Group theoretical analysis of the exciton structure of infrared bands predicts two components for molecular B modes and one component for molecular A modes in the high temperature phase. Below T c all the internal modes of benzil are expected to split into two components. Our experimental results show that the A molecular modes are resolved in a doublet structure in the low temperature phase whereas only one component is observed above T c. The doublet structure of infrared bands is studied as a function of temperature in the vicinity of T c. These splittings of crystal states in the low temperature phase are found to be described by a ¦T c - T¦ β law. The temperature dependence of the doublet structure of internal B modes is also studied below and above T c.

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