Mode-specific intermolecular vibrational energy transfer. II. Deuterated water and potassium selenocyanate mixture.
Mode-specific intermolecular vibrational energy transfer. II. Deuterated water and potassium selenocyanate mixture.
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DOI：
10.1063/1.3458825
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发表时间：
2010-07
期刊：
影响因子：
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通讯作者：
Hongtao Bian;Xiewen Wen;Jiebo Li;Junrong Zheng
中科院分区：
文献类型：
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作者：
Hongtao Bian;Xiewen Wen;Jiebo Li;Junrong Zheng
用多模二维红外光谱技术观察了氘代水（D（2）O）O-D伸缩的第一激发态（2635 cm（-1））到硒氰酸钾（KSeCN）CN伸缩的0-1跃迁（2075 cm（-1））的振动能量转移。尽管两种模式之间存在很大的能量不匹配（560 cm（-1）），但传输仍然非常有效，时间常数为20 ps。有效的能量转移可能是因为两个模式之间的大的激发耦合。实验确定耦合为176 cm（-1）。由Landau-Teller公式导出的近似解析方程用于计算能量传递率，所有参数均由实验确定。计算结果与实验数据定性一致。
Vibrational energy transfer from the first excited state (2635 cm(-1)) of the O-D stretch of deuterated water (D(2)O) to the 0-1 transition (2075 cm(-1)) of the CN stretch of potassium selenocyanate (KSeCN) in their 2.5:1 liquid mixture was observed with a multiple-mode two dimensional infrared spectroscopic technique. Despite the big energy mismatch (560 cm(-1)) between the two modes, the transfer is still very efficient with a time constant of 20 ps. The efficient energy transfer is probably because of the large excitation coupling between the two modes. The coupling is experimentally determined to be 176 cm(-1). An approximate analytical equation derived from the Landau-Teller formula is applied to calculate the energy transfer rate with all parameters experimentally determined. The calculation results are qualitatively consistent with the experimental data.