Vibrational Relaxation of O2(X3危g鈥?/sup>, v = 6鈥?) by Collisions with O2(X3危g鈥?/sup>, v = 0): Solution of the
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- 作者：Shinji Watanabe ; Hiroshi Kohguchi ; Katsuyoshi Yamasaki
- 刊名：The Journal of Physical Chemistry A
- 出版年：2012
- 出版时间：August 2, 2012
- 年：2012
- 卷：116
- 期：30
- 页码：7791-7796
- 全文大小：296K
- 年卷期：v.116,no.30(August 2, 2012)
- ISSN：1520-5215
文摘
The linear kinetic analysis called the integrated profiles method (IPM) makes it simple to analyze the multistep relaxation processes of vibrational manifold. The problem that plots for linear regression in the IPM analysis cannot be made, however, has been found in the study of self-relaxation of O2(X3危g鈥?/sup>, v = 6鈥?). The cause of the problem is the identical time-dependence of the populations of the adjacent vibrational levels. An addition of CF4 into the system made a difference in the time profiles and enabled us to make IPM analysis and determine the rate coefficients. In the experiments, a gaseous mixture of O3/O2/CF4 in an Ar carrier at 298 K was irradiated at 266 nm, and the direct photoproduct O2(X3危g鈥?/sup>, v = 6鈥?) from O3 was detected by laser-induced fluorescence (LIF) in the B3危u鈥?/sup>鈥揦3危g鈥?/sup> transition. Time-resolved LIF intensities of O2(X3危g鈥?/sup>, v) at various pressures of O2 and fixed pressure of CF4 were recorded. The resulting rate coefficients for v = 6鈥? correlate smoothly with those for v 鈮?5 and v 鈮?8 reported previously. The vibrational-level dependence (v = 2鈥?3) of the rate coefficients for relaxation of O2(X3危g鈥?/sup>, v) by O2 is accounted for by the balance between the harmonic transition probabilities and the energy defect in the V鈥揤 energy-transfer mechanism.