Department of Chemistry, Rice University, Houston, Texas 77005, USA.
J Chem Phys. 2010 Jul 21;133(3):034505. doi: 10.1063/1.3458825.
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.
用多模二维红外光谱技术观察到了氘化水（D2O）的 O-D 伸缩第一激发态（2635cm-1）与硒氰酸钾（KSeCN）的 CN 伸缩 0-1 跃迁（2075cm-1）之间的振动能量转移，两者在液体混合物中的比例为 2.5:1。尽管两种模式之间存在很大的能量不匹配（560cm-1），但转移仍然非常有效，时间常数为 20ps。这种有效的能量转移可能是由于两种模式之间的大激发耦合。实验确定耦合为 176cm-1。应用从 Landau-Teller 公式推导出的近似解析方程，用实验确定的所有参数计算能量转移速率。计算结果与实验数据定性一致。
