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通过O((3)P)+C(2)H(4)反应产生的振动激发态HCO的B(2)A(')-X(2)A(')探测

B(2)A(')-X(2)A(') detection of vibrationally excited HCO produced by the O((3)P)+C(2)H(4) reaction.

作者信息

Gardner Jennifer L, Miller Steven M

机构信息

Stewart Radiance Laboratory, Bedford, Massachusetts 01730, USA.

出版信息

J Chem Phys. 2004 Sep 22;121(12):5920-8. doi: 10.1063/1.1774984.

Abstract

The distribution of rotational and vibrational energy in HCO produced by the O((3)P)+C(2)H(4) reaction has been measured using laser-induced fluorescence detection via the B(2)A(')-X(2)A(') transition. Over a detection wavelength range of 248-290 nm, our experiments have shown that HCO is formed in both the ground state and in at least six vibrationally excited states with up to two quanta of energy in the C-O stretch and the bending mode. Dispersed fluorescence experiments were conducted to positively assign all of the HCO vibrational bands. The experiments confirmed that many bands, including the B(000)-X(000) band, are affected by overlap with other HCO bands. Spectral modeling was used to separate the contributions of overlapping HCO B-X bands and to determine a nascent HCO rotational temperature of approximately 600 K, corresponding to approximately 6% of the total energy from the O((3)P)+C(2)H(4) reaction. HCO vibrational distributions were determined for two different average collision energies and were fit with vibrational temperatures of 1850+/-80 K and 2000+/-100 K, corresponding to approximately 15% of the total energy. The observed Boltzmann distribution of vibrational energy in HCO indicates that HCO and CH(3) are formed by the dissociation of an energized intermediate complex.

摘要

通过O((3)P)+C(2)H(4)反应生成的HCO中转动能和振动能的分布,已使用经由B(2)A(')-X(2)A(')跃迁的激光诱导荧光检测进行了测量。在248 - 290 nm的检测波长范围内,我们的实验表明,HCO在基态以及至少六个振动激发态中形成,在C - O伸缩和弯曲模式中具有高达两个能量量子。进行了色散荧光实验以明确归属所有的HCO振动带。实验证实,许多谱带,包括B(000)-X(000)谱带,受到与其他HCO谱带重叠的影响。使用光谱建模来分离重叠的HCO B - X谱带的贡献,并确定初生HCO转动温度约为600 K,对应于O((3)P)+C(2)H(4)反应总能量的约6%。针对两种不同的平均碰撞能量确定了HCO振动分布,并拟合得到振动温度为1850±80 K和2000±100 K,对应于总能量的约15%。在HCO中观察到的振动能的玻尔兹曼分布表明,HCO和CH(3)是由一个激发的中间复合物解离形成的。

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