College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China.
J Chem Phys. 2011 Oct 7;135(13):134304. doi: 10.1063/1.3644776.
Four internal-rotation/vibration bands of the Ne-D(2)O complex have been measured in the v(2) bend region of D(2)O using a tunable infrared diode laser spectrometer to probe a slit supersonic expansion. Three ortho bands are excited from the ground state Σ(0(00)) to the Σ and Π(1(11), υ(2) = 1) internal rotor states and the n = 1, Σ(0(00), υ(2) = 1) stretching-internal rotor combination state. Strong perturbations between the excited vibrational states are evident. The observed spectra are analyzed separately with a three-state J-dependent Coriolis plus J-independent angular-radial coupling model [M. J. Weida and D. J. Nesbitt, J. Chem. Phys. 106, 3078 (1997)] and a three-state Coriolis coupling model [R. C. Cohen and R. J. Saykally, J. Chem. Phys. 95, 7891 (1991)]. The former model works more successfully than the latter. Molecular constants for the ground and excited vibrational states of ortho (20)Ne-D(2)O isotopomer as well as the Coriolis and angular-radial coupling constants are determined accurately. The van der Waals stretching frequency is estimated to be ν(s) = 24.85 cm(-1) in the ground state and decreases to about 20.8 cm(-1) upon vibrational excitation of the D(2)O bend.
已使用可调谐红外二极管激光光谱仪在 D2O 的 v(2)弯曲区域测量了 Ne-D(2)O 络合物的四个内旋转/振动带，以探测狭缝超声速膨胀。三个正态Σ(0(00))到Σ和Π(1(11), υ(2) = 1)内转子态和 n = 1, Σ(0(00), υ(2) = 1)拉伸-内转子组合态的激发。在激发的振动态之间存在明显的强扰动。观察到的光谱分别用三个态 J 相关的科里奥利加 J 独立的角径耦合模型 [M. J. Weida 和 D. J. Nesbitt, J. Chem. Phys. 106, 3078 (1997)] 和三个态科里奥利耦合模型 [R. C. Cohen 和 R. J. Saykally, J. Chem. Phys. 95, 7891 (1991)] 进行了单独分析。前者模型比后者模型更成功。准确确定了正(20)Ne-D(2)O 同位素的基态和激发振动态以及科里奥利和角径耦合常数的分子常数。在基态下，范德华拉伸频率估计为 ν(s) = 24.85 cm(-1)，在 D2O 弯曲的振动激发下降至约 20.8 cm(-1)。
