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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photodissociation Dynamics of Acetic Acid and Trifluoroacetic Acid at 193 nm
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Photodissociation Dynamics of Acetic Acid and Trifluoroacetic Acid at 193 nm

机译：乙酸和三氟乙酸在193 nm处的光解离动力学

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摘要

Photodissociation dynamics of acetic acid and trifluoroacetic acid at 193 nm have been investigated by measuring laser-induced fluorescence spectra of OH fragments. The OH fragments are produced exclusively in the ground electronic state. The measured energy distributions among the fragments are f_r(OH)=0.05, f_t=0.42, f_(int)(Ac)=0.53 and f_r(OH)=0.05, f_t=0.33, and f_(int)(Fac)=0.62, for acetic and trifluoroacetic acid, respectively, and negligible vibrational excitation in the OH fragments was observed. The dissociation does not depend on the polarization of the dissociating light. It was concluded from the measured energy distribution and no polarization dependence that the electronic transition at 193 nm leads the parent molecule to the singlet excited surface, and the dissociation takes place along the triplet surface with an exit channel barrier. From the estimated internal energies in the acetyl radicals, the lifetimes of the acetyl radicals are estimated from the RRKM theory.
机译：乙酸和三氟乙酸在193 nm处的光解离动力学已通过测量OH片段的激光诱导荧光光谱进行了研究。 OH片段仅在基态电子状态下产生。片段之间测得的能量分布为f_r（OH）= 0.05，f_t = 0.42，f_（int）（Ac）= 0.53和f_r（OH）= 0.05，f_t = 0.33和f_（int）（Fac）= 0.62分别为乙酸和三氟乙酸，并且在OH片段中观察到微不足道的振动激发。离解不取决于离解光的偏振。从测得的能量分布和无极化依赖性得出的结论是，在193 nm处的电子跃迁将母体分子引导至单重态激发表面，并且解离沿着三重态表面发生，并带有出口通道势垒。根据估计的乙酰基内部能量，可以根据RRKM理论估计乙酰基的寿命。

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