Large Angular Jump Mechanism Observed for Hydrogen Bond Exchange in Aqueous Perchlorate Solution

被引：181

作者：

Ji, Minbiao ^{[1
,2
]}

Odelius, Michael ^{[3
]}

Gaffney, K. J. ^{[1
]}

机构：

[1] Stanford Univ, SLAC Natl Accelerator Lab, PULSE Inst Ultrafast Energy Sci, Stanford, CA 94305 USA

[2] Stanford Univ, Dept Phys, Stanford, CA 94305 USA

[3] Stockholm Univ, AlbaNova Univ Ctr, SE-10691 Stockholm, Sweden

来源：

SCIENCE | 2010年 / 328卷 / 5981期

基金：

瑞典研究理事会;

关键词：

INFRARED-SPECTROSCOPY; ULTRAFAST DYNAMICS; MOLECULAR-DYNAMICS; LIQUID WATER; 2D IR; REORIENTATION; 3RD-ORDER; 2D-IR; TIME;

D O I：

10.1126/science.1187707

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The mechanism for hydrogen bond (H-bond) switching in solution has remained subject to debate despite extensive experimental and theoretical studies. We have applied polarization-selective multidimensional vibrational spectroscopy to investigate the H-bond exchange mechanism in aqueous NaClO(4) solution. The results show that a water molecule shifts its donated H-bonds between water and perchlorate acceptors by means of large, prompt angular rotation. Using a jump-exchange kinetic model, we extracted an average jump angle of 49 +/- 4 degrees, in qualitative agreement with the jump angle observed in molecular dynamics simulations of the same aqueous NaClO(4) solution.

引用

页码：1003 / 1005

页数：3

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