When the crystal grows from solution,a sharp variated fluid layer of the solute concentration exists against crystal surface.The sharp variated fluid layer is defined the boundary layer in crystal growth.The molecular structure of the boundary layers plays a key role in crystal composition,morphology,growth rate and crystal growth mechanism.However,owing to the lacking of suitable probe technique,it is difficult to obtain the information of the moving construction of the boundary layers.Here,the laser Raman Microprobe combining with holographic phase contrast interferometric microphotography is used to probe in situ the molecular structure of the boundary layers during the crystal growth processes of KH 2PO 4(KDP) and KD 2PO 4(DKDP).In supersaturations ranging from 1% to 14%,Raman scattering states at the different positions within the boundary layers have been investigated,and compared with the bands of different concentration solutions alone using laser Raman spectroscopy between 600 and 1350cm -1 .The changes in band parameters of the phosphates within the boundary layers of crystal growth are different from those in solution alone.The influence of the solution concentration on the band parameters of anion phosphate within the layers is nonlinear.With increasing supersaturation,the full width at half height of the P=O 2 symmetric stretch band increases.The new 918(938)cm -1 H(D)O P OH(D) asymmetric stretch,1120(DKDP 1200)cm -1 O P O asymmetric stretch,and extremely weak 1210cm -1 P O H in plane deformation bands appear in the characteristic boundary layers.These new bands show that the cations have direct effects on the phosphate group(aggregates).Under the driving of concentration gradient field of supersaturation,the effects of cations cause the changes of O P O bond angle,atomic charge redistribution,and lead to readjust geometry of anion phosphate group and desolvation.The trend of readjust is close to the geometry of the crystal structure unit and the formation of the cations phosphate crystallization unit.
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