Optical Spectroscopy of Crystal Nucleation One Nucleus at a Time

Abstract

<p>Crystallization is an important process in a wide range of disciplines from fundamental science to industrial application. Despite the importance of controlling the crystallization and its morphology (<i>e.g.</i> polymorphism), the lack of microscopic description of crystal nucleation often limits the rational approach to its engineering and control. The biggest challenge to experimentally track the nucleus formation is the stochastic and heterogeneous nature of the nucleation occurring at nanometer scale. To overcome this challenge, we developed a method we call “Single Nucleus Spectroscopy” or SNS and use it to follow the formation of single crystal glycine nucleus by Raman spectroscopy at 46 ms time resolution. The spectral evolution was analyzed by non-supervised spectral decomposition algorithm which unraveled the Raman spectrum of prenucleation aggregates. In order to gain microscopic insights into the structure of these aggregates we have established a direct comparison between the experiments and theoretical works. The outcome of our analysis is a new hypothesis of glycine crystal nucleation mechanism.<br></p>

Pseudopolymorphism of Sodium Acetate in Supersaturated Aqueous Solution Induced by Focused Irradiation with Ultrashort Laser Pulses

“…Another photophysical approach is "optical trapping-induced crystallization (OTIC)" where condensation of solute molecules (and/or clusters) at laser focus via optical trapping triggers nucleation. 11,12 Noteworthy, the studies of NPLIN and OTIC also demonstrated the polarization-dependent polymorphism, 2−4 of which mechanism has been discussed based on interactions between polarizability tensors of solute molecules (and/or clusters) and photoelectric fields and/or difference in bubble formation behavior with polarization.…”