Kobayashi Yusuke, Inokuchi Yoshiya, Ebata Takayuki
Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8526, Japan.
J Chem Phys. 2008 Apr 28;128(16):164319. doi: 10.1063/1.2913157.
Infrared photodissociation spectra of (CS(2))(n) (+) and (CS(2))(n) (-) with n=3-10 are measured in the 1100-2000 cm(-1) region. All the (CS(2))(n) (+) clusters exhibit three bands at approximately 1410, approximately 1490, and approximately 1540 cm(-1). The intensity of the 1540 cm(-1) band relative to those of the other bands increases with increasing the cluster size, indicating that the band at 1540 cm(-1) is assignable to the antisymmetric CS stretching vibration of solvent CS(2) molecules in the clusters. On the basis of density functional theory calculations, the 1410 and 1490 cm(-1) bands of (CS(2))(n) (+) are assigned to CS stretching vibrations of the C(2)S(4) (+) cation core with a C(2) form. The (CS(2))(n) (-) clusters show two bands at around 1215 and 1530 cm(-1). Similar to the case of cation clusters, the latter band is ascribed to the antisymmetric CS stretching vibration of solvent CS(2) molecules. Vibrational frequency analysis of CS(2) (-) and C(2)S(4) (-) suggests that the 1215 cm(-1) band is attributed to the antisymmetric CS stretching vibration of the CS(2) (-) anion core with a C(2v) structure.
测量了n = 3 - 10时(CS₂)ₙ⁺和(CS₂)ₙ⁻在1100 - 2000 cm⁻¹区域的红外光解离光谱。所有(CS₂)ₙ⁺团簇在约1410、约1490和约1540 cm⁻¹处呈现出三个谱带。1540 cm⁻¹谱带相对于其他谱带的强度随团簇尺寸增大而增加，这表明1540 cm⁻¹处的谱带可归属于团簇中溶剂CS₂分子的反对称CS伸缩振动。基于密度泛函理论计算，(CS₂)ₙ⁺的1410和1490 cm⁻¹谱带归属于具有C₂形式的C₂S₄⁺阳离子核的CS伸缩振动。(CS₂)ₙ⁻团簇在约1215和1530 cm⁻¹处显示出两个谱带。与阳离子团簇的情况类似，后一个谱带归因于溶剂CS₂分子的反对称CS伸缩振动。CS₂⁻和C₂S₄⁻的振动频率分析表明，1215 cm⁻¹谱带归因于具有C₂ᵥ结构的CS₂⁻阴离子核的反对称CS伸缩振动。
