Temperature Effect on the Absorption Spectrum of the Hydrated Electron Paired with a Lithium Cation in Deuterated Water
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- 作者：Mingzhang Lin ; Yuta Kumagai ; Isabelle Lampre ; Franç ; ois-Xavier Coudert ; Yusa Muroya ; Anne Boutin ; Mehran Mostafavi ; Yosuke Katsumura
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：May 10, 2007
- 年：2007
- 卷：111
- 期：18
- 页码：3548 - 3553
- 全文大小：143K
- 年卷期：v.111,no.18(May 10, 2007)
- ISSN：1520-5215
文摘
The absorption spectra of the hydrated electron in 1.0 to 4.0 M LiCl or LiClO4 deuterated water solutionswere measured by pulse radiolysis techniques from room temperature to 300 
C at a constant pressure of 25MPa. The results show that when the temperature is increased and the density is decreased, the absorptionspectrum of the electron in the presence of a lithium cation is shifted to lower energies. Quantum classicalmolecular dynamics (QCMD) simulations of an excess electron in bulk water and in the presence of a lithiumcation have been performed to compare with the experimental results. According to the QCMD simulations,the change in the shape of the spectrum is due to one of the three p-like excited states of the solvated electrondestabilized by core repulsion. The study of s 
p transition energies for the three p-excited states revealsthat for temperatures higher than room temperature, there is a broadening of each individual s p absorptionband due to a less structured water solvation shell.
C at a constant pressure of 25MPa. The results show that when the temperature is increased and the density is decreased, the absorptionspectrum of the electron in the presence of a lithium cation is shifted to lower energies. Quantum classicalmolecular dynamics (QCMD) simulations of an excess electron in bulk water and in the presence of a lithiumcation have been performed to compare with the experimental results. According to the QCMD simulations,the change in the shape of the spectrum is due to one of the three p-like excited states of the solvated electrondestabilized by core repulsion. The study of s p transition energies for the three p-excited states revealsthat for temperatures higher than room temperature, there is a broadening of each individual s p absorptionband due to a less structured water solvation shell.