| 145525-93-5

• 分子结构分类: 有机化合物
• CAS: 145525-93-5
• 化学式: Ar₂*FH
• 分子量: 99.9023
• InChiKey: VVMJBSKBZJUNPE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.15
• 重原子数：
  3.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  氢氟酸 、 氩 以 neat (no solvent, gas phase) 为溶剂， 生成
  参考文献：
  名称：

  Laser-induced fluorescence spectroscopy of Ar2HF at vHF=3: An examination of three-body forces

  摘要：

  The vibrational spectrum of Ar2HF in the 11 320–11 430 cm−1 region is recorded by intracavity laser-induced fluorescence. The intramolecular vibrational state, Σ0, in combination with the intermolecular vibrations, assigned as Πin-plane, Πout-of-plane and Σ1, of the complex have been observed. The Σ0 state correlates adiabatically with j=0 of HF (v=3); the Πin-plane, Πout-of-plane, and Σ1 states correlate adiabatically with j=1 of HF (v=3), respectively. We have determined the vibrational band origins (and rotational constants) of ν0=11 323.784 cm−1 (A=0.120 15, B=0.058 30, C=0.038 94 cm−1), ν0=11 387.730 cm−1 (A=0.122 68, B=0.057 05, C=0.038 42 cm−1), ν0=11 426.815 cm−1 (A=0.120 27, B=0.058 15, C=0.038 71 cm−1) and ν0=11 427.400 cm−1 (A=0.120 26, B=0.058 15, C=0.038 71 cm−1) for Σ0, Πin-plane, Πout-of-plane, and Σ1 states, respectively. The vibrational red shift for the pure HF stretch from vHF=0–3 is 49.023 cm−1. The in-plane and out-of-plane bending frequencies are 63.947 and 103.031 cm−1. The Σ1 state, which may be viewed as the Ar2FH structure is located 103.616 cm−1 above the Ar2HF Σ0 state. The spectral line shapes appear to be well fitted by a Doppler profile with FWHM≈120 MHz, indicating that the predissociation linewidths have a Lorentzian component of less than 10 MHz. These results are compared with those of Farrell and Nesbitt [J. Chem. Phys. 105, 9421 (1996)] for vHF=1. The present experimental data set is also compared with the quantitative predictions by Ernesti and Hutson [Phys. Rev. A 51, 239 (1995)] and therefore serves as a rigorous test for modeling nonadditivity of intermolecular interactions and their vibrational dependence. These comparisons show that the vibrational dependence of three-body terms is accurate in the region of potential minimum. For configurations far from the energy minimum, appreciable discrepancies appear to exist. The vibrational variation of the Πin-plane bending frequency is relatively poorly predicted, which strongly suggests the inadequacy in the present modeling of the intriguing nonadditive forces for this prototypical system.

  DOI：

  10.1063/1.474947

文献信息

• Probing three‐body intermolecular forces: Near‐infrared spectroscopy of Ar₂HF and Ar₂DF van der Waals modes
  作者：John T. Farrell、David J. Nesbitt

  DOI：10.1063/1.472777

  日期：1996.12

  Four intermolecular vibrational states of the weakly bound complexes Ar2HF and Ar2DF have been studied via high-resolution infrared spectroscopy. The vibrations are accessed as combination bands built on the v=1 HF or DF intramolecular stretch. These van der Waals vibrational states correlate adiabatically with j=1 motion of a hindered HF/DF rotor, corresponding to librational motion either in, or out of, the molecular plane. The vibrational origins of the Ar2HF in-plane and out-of-plane bends are 4008.9665(24) and 4035.174 41(86) cm−1, respectively, which are 62.374 and 88.582 cm−1 above the origin of the intermolecular ground state in the vHF=1 manifold. For Ar2DF, the in-plane and out-of-plane origins are 2939.836 63(4) and 2967.101 29(5) cm−1, respectively, which correspond to intermolecular bending frequencies in the vDF=1 manifold of 44.852 and 72.117 cm−1. Two-dimensional angular calculations are presented which solve for the hindered rotor HF/DF eigenfunctions and eigenvalues on a pairwise additive potential constructed using a rigid Ar2 framework; the predicted bending frequencies reproduce the correct energy ordering of the vibrational levels, but are systematically greater than experimentally observed. Rigorous full five-dimensional theoretical calculations of the intermolecular vibrational frequencies by Ernesti and Hutson [Phys. Rev. A 51 239 (1995)] on the full pairwise additive surface are found to be as much as 11% higher than the experimental values, indicating the presence of three-body repulsive contributions to the true angular potential. Inclusion of conventional three-body dispersion and induction terms can only account for a minority (≊1/3) of the observed discrepancies. The majority (≊2/3) of the vibrational shifts can be attributed to three-body ‘‘exchange’’ effects, i.e., the strongly anisotropic interaction of the HF/DF dipole with an exchange quadrupole formed by Ar–Ar. Inclusion of all three nonadditive terms (dispersion, induction, and exchange) improves the agreement with experiment by up to an order of magnitude.