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DOI	10.1073/pnas.1910691116
	Solvent fluctuations in the solvation shell determine the activation barrier for crystal growth rates
	Dighe A.V.; Singh M.R.
发表日期	2019
ISSN	0027-8424
起始页码	23954
结束页码	23959
卷号	116 期号:48
英文摘要	Solution crystallization is a common technique to grow advanced, functional crystalline materials. Supersaturation, temperature, and solvent composition are known to influence the growth rates and thereby properties of crystalline materials; however, a satisfactory explanation of how these factors affect the activation barrier for growth rates has not been developed. We report here that these effects can be attributed to a previously unrecognized consequence of solvent fluctuations in the solvation shell of solute molecules attaching to the crystal surface. With increasing supersaturation, the average hydration number of the glutamic acid molecule decreases and can reach an asymptotic limit corresponding to the number of adsorption sites on the molecule. The hydration number of the glutamic acid molecule also fluctuates due to the rapid exchange of solvent in the solvation shell and local variation in the supersaturation. These rapid fluctuations allow quasi-equilibrium between fully solvated and partially desolvated states of molecules, which can be used to construct a double-well potential and thereby to identify the transition state and the required activation barrier. The partially desolvated molecules are not stable and can attach spontaneously to the crystal surface. The activation barrier versus hydration number follows the Evans–Polanyi relation. The predicted absolute growth rates of the α-glutamic acid crystal at lower supersaturations are in reasonable agreement with the experimental observations. © 2019 National Academy of Sciences. All rights reserved.
英文关键词	Growth rate; Molecular dynamics; Organic crystals; Solution crystallization
语种	英语
scopus关键词	glutamic acid; solvent; adsorption kinetics; Article; crystallization; equilibrium constant; growth rate; hydration; molecular dynamics; phase transition; priority journal; solute; solvate; solvation; surface property
来源期刊	Proceedings of the National Academy of Sciences of the United States of America
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/160331
作者单位	Dighe, A.V., Department of Chemical Engineering, University of Illinois at Chicago, Chicago, IL 60607, United States; Singh, M.R., Department of Chemical Engineering, University of Illinois at Chicago, Chicago, IL 60607, United States
推荐引用方式 GB/T 7714	Dighe A.V.,Singh M.R.. Solvent fluctuations in the solvation shell determine the activation barrier for crystal growth rates[J],2019,116(48).
APA	Dighe A.V.,&Singh M.R..(2019).Solvent fluctuations in the solvation shell determine the activation barrier for crystal growth rates.Proceedings of the National Academy of Sciences of the United States of America,116(48).
MLA	Dighe A.V.,et al."Solvent fluctuations in the solvation shell determine the activation barrier for crystal growth rates".Proceedings of the National Academy of Sciences of the United States of America 116.48(2019).