Real-Time Pursuit of Crystal Growth by Millisecond Time-Resolved Multichannel Fourier Transform Infrared Spectroscopy

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Abstract:

The surface (about 130 molecular layers) of an oriented thin crystal of decanoic acid was subjected to sudden melting by a laser-induced temperature jump (T-jump), and the process of subsequent crystal re-growth was monitored by millisecond time-resolved multichannel Fourier transform infrared spectroscopy. The gauche - trans structural change of the alkane part of the molecule has been probed by the CH stretch bands in the 2800-3000 cm -1 region. The change in the molecular orientation has been detected by the OH stretch band around 3065 cm -1. The recovery curves for the CH antisymmetric stretch and the OH2 stretch bands are markedly different from each other in the first 200 ms, suggesting that the gauche - trans structural changes precedes the crystal re-growth. After 500 ms, the recovery curves become identical. This result means that the rate of the gauche to the trans structural change is equal to the rate of the recovery of the molecular orientation. It is highly likely that a fast equilibrium is attained between the gauche and the trans conformations in the liquid phase after 500 ms from the sudden melting and that the crystal re-growth takes place solely via the all- trans structure in the liquid phase.
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