DOI: 10.1073/pnas.2017214117
论文题名: Absolute ion hydration free energy scale and the surface potential of water via quantum simulation
作者: Shi Y. ; Beck T.L.
刊名: Proceedings of the National Academy of Sciences of the United States of America
ISSN: 0027-8424
出版年: 2020
卷: 117, 期: 48 起始页码: 30151
结束页码: 30158
语种: 英语
英文关键词: Single-ion thermodynamics | hydration free energy | DFT | ab initio quantum molecular dynamics | surface potential
英文摘要: With a goal of determining an absolute free energy scale for ion hydration, quasi-chemical theory and ab initio quantum mechanical simulations are employed to obtain an accurate value for the bulk hydration free energy of the Na+ ion. The free energy is partitioned into three parts: 1) the inner-shell or chemical contribution that includes direct interactions of the ion with nearby waters, 2) the packing free energy that is the work to produce a cavity of size λ in water, and 3) the long-range contribution that involves all interactions outside the inner shell. The interfacial potential contribution to the free energy resides in the long-range term. By averaging cation and anion data for that contribution, cumulant terms of all odd orders in the electrostatic potential are removed. The computed total is then the bulk hydration free energy. Comparison with the experimentally derived real hydration free energy produces an effective surface potential of water in the range −0.4 to −0.5 V. The result is consistent with a variety of experiments concerning acid–base chemistry, ion distributions near hydrophobic interfaces, and electric fields near the surface of water droplets. © 2020 National Academy of Sciences. All rights reserved. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/163361
Appears in Collections: 气候变化与战略
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作者单位: Shi, Y., Department of Chemistry, University of Cincinnati, Cincinnati, OH 45221, United States; Beck, T.L., Department of Chemistry, University of Cincinnati, Cincinnati, OH 45221, United States
Recommended Citation:
Shi Y.,Beck T.L.. Absolute ion hydration free energy scale and the surface potential of water via quantum simulation[J]. Proceedings of the National Academy of Sciences of the United States of America,2020-01-01,117(48)