The Local Structure of Liquid Water from Raman Spectroscopy

LIN Ke; LIU Shilin; ZHOU Xiaoguo; LUO Yi

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The Local Structure of Liquid Water from Raman Spectroscopy

LIN Ke #,LIU Shilin *,ZHOU Xiaoguo,LUO Yi

Hefei National Laboratory for Physical Sciences at the Microscale， Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, China

*Correspondence author

#Submitted by

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Funding: National Key Basic Research Special Foundation （No.NKBRSF, 2010CB923300), the National Natural Science Foundation of China）

Opened online:27 January 2014

Accepted by: none

Citation: LIN Ke,LIU Shilin,ZHOU Xiaoguo.The Local Structure of Liquid Water from Raman Spectroscopy[OL]. [27 January 2014] http://en.paper.edu.cn/en_releasepaper/content/4582073

The local structure of liquid water has been systematically investigated with Raman spectroscopy in a temperature range of 10 oC to 70 oC. It is found five spectra components respond differently to the temperatures. Comparison with the Raman spectra of little water in some organic solvents, the unbonded free -OH (-OD) stretching vibration band has been observed at ~3630 cm-1 (~2655 cm-1) in liquid water. With the aid of the theoretical calculations of larger kinds of water with different hydrogen bond pattern, the other strong spectra components have been identified and assigned to the -OH (-OD) stretching vibration band of the water molecules that form different kinds of hydrogen bond structure. Below the free OH stretching region, the four components were assigned as the vibration of the water molecules with the local structure of donor-donor-acceptor (DDA), distorted donor-donor-acceptor-acceptor (DDAA), ordered DDAA, and donor-acceptor- acceptor (DAA) configurations. Furthermore, the distribution of these kinds of water molecules and its temperature dependence have been derived from the reasonable spectral decomposition, which lead to the conclusion that the average number of shydrogen bond per water molecules in liquid is decreased from ~3.8 at 10 oC to ~3.5 at 70 oC.

Keywords:chemical dynamics; water;local structure;average HB number;Raman spectroscopy

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