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首页> 外文期刊>The Journal of Chemical Physics >The C_3-bending vibrational levels of the C_3-Kr and C_3-Xe van der Waals complexes studied by their ?-X? electronic transitions and by ab initio calculations
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The C_3-bending vibrational levels of the C_3-Kr and C_3-Xe van der Waals complexes studied by their ?-X? electronic transitions and by ab initio calculations

机译：C_3-Kr和C_3-Xe van der Waals配合物的C_3弯曲振动能级由它们的α-X？研究。电子过渡和从头算

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摘要

Fluorescence excitation spectra and wavelength-resolved emission spectra of the C_3-Kr and C_3-Xe van der Waals (vdW) complexes have been recorded near the 2~(2-)_0, 2~2_0, 2~(4-)_0, and 1~1_0 bands of the Au1-X1g+system of the C_3 molecule. In the excitation spectra, the spectral features of the two complexes are red-shifted relative to those of free C_3 by 21.9-38.2 and 34.3-36.1 cm~(-1), respectively. The emission spectra from the A state of the Kr complex consist of progressions in the two C_3-bending vibrations (_(2, 4)), the vdW stretching (_3), and bending vibrations (_6), suggesting that the equilibrium geometry in the X? state is nonlinear. As in the Ar complex Zhang, J. Chem. Phys. 120, 3189 (2004), the C_3-bending vibrational levels of the Kr complex shift progressively to lower energy with respect to those of free C_3 as the bending quantum number increases. Their vibrational structures could be modeled as perturbed harmonic oscillators, with the dipole-induced dipole terms of the Ar and Kr complexes scaled roughly by the polarizabilities of the Ar and Kr atoms. Emission spectra of the Xe complex, excited near the ?, 2~(2-) level of free C_3, consist only of progressions in even quanta of the C_3-bending and vdW modes, implying that the geometry in the higher vibrational levels (b_(end) ≥ 4, E_(vib) ≥ 328 cm~(-1)) of the X? state is (vibrationally averaged) linear. In this structure the Xe atom bonds to one of the terminal carbons nearly along the inertial a-axis of bent C _3. Our ab initio calculations of the Xe complex at the level of CCSD(T)aug-cc-pVTZ (C) and aug-cc-pVTZ-PP (Xe) predict that its equilibrium geometry is T-shaped (as in the Ar and Kr complexes), and also support the assignment of a stable linear isomer when the amplitude of the C3 bending vibration is large (u_4 ≥ 4).
机译：C_3-Kr和C_3-Xe van der Waals（vdW）配合物的荧光激发光谱和波长分辨的发射光谱已记录在2〜（2-）_ 0、2〜2_0、2〜（4-）_ 0， C_3分子的Au1-X1g +系统的1〜1_0条带。在激发光谱中，两个配合物的光谱特征相对于游离C_3的光谱特征分别发生了21.9-38.2和34.3-36.1 cm〜（-1）的红移。 Kr配合物的A状态的发射光谱包括两个C_3弯曲振动（_（2，4）），vdW拉伸（_3）和弯曲振动（_6）的级数，这表明在X？状态是非线性的。如在Ar络合物中，张，化学。物理在第120卷，第3189页（2004）中，随着弯曲量子数的增加，Kr复合物的C_3弯曲振动能级相对于自由C_3的振动能逐渐降低。可以将它们的振动结构建模为扰动的谐波振荡器，其中Ar和Kr络合物的偶极子诱发的偶极子项大致由Ar和Kr原子的极化率缩放。 Xe络合物的发射光谱在自由C_3的α，2〜（2-）水平附近激发，仅由C_3弯曲和vdW模式的偶数量子级数组成，这意味着在较高振动水平下的几何形状（b_ （末端）≥4，X的E_（vib）≥328 cm〜（-1））？状态是（振动平均）线性的。在这种结构中，Xe原子几乎沿着弯曲C _3的惯性a轴键合到一个末端碳上。我们在CCSD（T）aug-cc-pVTZ（C）和aug-cc-pVTZ-PP（Xe）的水平上对Xe络合物的从头算计算表明其平衡几何形状为T形（如Ar和Kr络合物），并且当C3弯曲振动的幅度较大（u_4≥4）时，也支持分配稳定的线性异构体。

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