Kinetic Study of Vibrational Energy Transfer from a Wide Range of Vibrational Levels of O2(X3Σg−, v = 6−12) to CF4

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• 作者：Shinji Watanabe ; Hidekazu Fujii ; Hiroshi Kohguchi ; Takayuki Hatano ; Ikuo Tokue ; Katsuyoshi Yamasaki
• 刊名：Journal of Physical Chemistry A
• 出版年：2008
• 出版时间：October 2, 2008
• 年：2008
• 卷：112
• 期：39
• 页码：9290-9295
• 全文大小：226K
• 年卷期：v.112,no.39(October 2, 2008)
• ISSN：1520-5215

文摘

A wide range of vibrational levels of O₂(X³Σ_g⁻, v = 6−13) generated in the ultraviolet photolysis of O₃ was selectively detected by the laser-induced fluorescence (LIF) technique. The time-resolved LIF-excited B³Σ_u⁻−X³Σ_g⁻ system in the presence of CF₄ has been recorded and analyzed by the integrated profiles method (IPM). The IPM permitted us to determine the rate coefficients k_v^CF₄ for vibrational relaxation of O₂(X³Σ_g⁻, v = 6−12) by collisions with CF₄. Energy transfer from O₂ (v = 6−12) to CF₄ is surprisingly efficient compared to that of other polyatomic relaxation partners studied so far. The k_v^CF₄ increases with vibrational quantum number v from [1.5 ± 0.2(2σ)] × 10⁻¹² for v = 6 to [7.3 ± 1.5(2σ)] × 10⁻¹¹ for v = 12, indicating that the infrared-active ν₃ vibrational mode of CF₄ mainly governs the energy transfer with O₂(X³Σ_g⁻, v = 6−12). The correlation between the rate coefficients and fundamental infrared intensities has been discussed based on a comparison of the efficiency of energy transfer by several collision partners.