Ultrafast hydrogen-bond dynamics in the infrared spectroscopy of water

被引：875

作者：

Fecko, CJ

Eaves, JD

Loparo, JJ

Tokmakoff, A ^{[1
]}

Geissler, PL

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

[2] MIT, George R Harrison Spect Lab, Cambridge, MA 02139 USA

来源：

SCIENCE | 2003年 / 301卷 / 5640期

关键词：

D O I：

10.1126/science.1087251

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：

We investigated rearrangements of the hydrogen-bond network in water by measuring fluctuations in the OH-stretching frequency of HOD in liquid D2O with femtosecond infrared spectroscopy. Using simulations of an atomistic model of water, we relate these frequency fluctuations to intermolecular dynamics. The model reveals that OH frequency shifts arise from changes in the molecular electric field that acts on the proton. At short times, vibrational dephasing reflects an underdamped oscillation of the hydrogen bond with a period of 170 femtoseconds. At longer times, vibrational correlations decay on a 1.2-picosecond time scale because of collective structural reorganizations.

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收藏

页码：1698 / 1702

页数：5

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