化学
质子
氢键
质子输运
化学物理
磷酸
分子内力
低势垒氢键
电导率
氢
极化率
计算化学
物理化学
分子
立体化学
膜
有机化学
物理
量子力学
生物化学
作者
Linas Vilčiauskas,Mark E. Tuckerman,Gabriel Bester,Stephen J. Paddison,Klaus‐Dieter Kreuer
出处
期刊:Nature Chemistry
[Springer Nature]
日期:2012-04-22
卷期号:4 (6): 461-466
被引量:450
摘要
Neat liquid phosphoric acid (H(3)PO(4)) has the highest intrinsic proton conductivity of any known substance and is a useful model for understanding proton transport in other phosphate-based systems in biology and clean energy technologies. Here, we present an ab initio molecular dynamics study that reveals, for the first time, the microscopic mechanism of this high proton conductivity. Anomalously fast proton transport in hydrogen-bonded systems involves a structural diffusion mechanism in which intramolecular proton transfer is driven by specific hydrogen bond rearrangements in the surrounding environment. Aqueous media transport excess charge defects through local hydrogen bond rearrangements that drive individual proton transfer reactions. In contrast, strong, polarizable hydrogen bonds in phosphoric acid produce coupled proton motion and a pronounced protic dielectric response of the medium, leading to the formation of extended, polarized hydrogen-bonded chains. The interplay between these chains and a frustrated hydrogen-bond network gives rise to the high proton conductivity.
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