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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Isotopically Selective Infrared Multiphoton Dissociation of 2,3-Dihydropyran
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Isotopically Selective Infrared Multiphoton Dissociation of 2,3-Dihydropyran

机译：2,3-二氢吡喃的同位素选择性红外多光子解离

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摘要

Oxygen isotopic selectivity on infrared multiphoton dissociation of 2,3-dihydropyran has been studied by the examination of the effects of excitation frequency, laser fluence, and gas pressure on the dissociation probability of 2,3-dihydropyran and isotopic composition of products. Oxygen-18 was enriched in a dissociation product: 2-propenal. The enrichment factor of ~(18)O and the dissociation probability were measured at a laser frequency between 1033.5 and 1057.3 cm~(-1), the laser fluence of 2.2—2.3 J/cm~2, and the 2,3-dihydropyran pressure of 0.27 kPa. The dissociation probability decreases as the laser frequency being detuned from the absorption peak of 2,3-dihydropyran around 1081 cm~(-1). On the other hand, the enrichment factor increases with detuning the frequency. The enrichment factor of ~(18)O increases with increasing the 2,3-dihydropyran pressure at the laser fluence of 2.7 J/cm~2 or less and the laser frequency of 1033.5 cm~(-1), whereas the yield of 2-propenal decreases with increasing the pressure. A very high enrichment factor of 751 was obtained by the irradiation of 0.53 kPa of 2,3-dihydropyran at 2.1 J/cm~2. Collisional effect of vibrationally excited molecules with ambient molecules on isotopic selectivity is discussed on the basis of a rate equation model including a collisional vibrational de-excitation process.
机译：通过研究激发频率，激光通量和气压对2，3-二氢吡喃解离几率和产物同位素组成的影响，研究了氧同位素选择性对2，3-二氢吡喃的红外多光子解离的影响。氧18富含解离产物：2-丙醛。在1033.5和1057.3 cm〜（-1）的激光频率，2.2-2.3 J / cm〜2的激光通量和2,3-二氢吡喃下测量〜（18）O的富集因子和解离几率压力为0.27 kPa。解离几率随着激光频率从2,3-二氢吡喃的吸收峰在1081 cm〜（-1）附近失谐而降低。另一方面，富集因子随着频率的失谐而增加。 〜（18）O的富集因子在2.7 J / cm〜2或更低的激光能量密度和1033.5 cm〜（-1）的激光频率下随着2,3-二氢吡喃压力的增加而增加，而产率为2 -丙烯随压力的增加而减少。通过以2.1 J / cm〜2辐射0.53 kPa的2,3-二氢吡喃得到非常高的751富集因子。基于包括碰撞振动去激励过程的速率方程模型，讨论了振动激发的分子与周围分子的碰撞对同位素选择性的影响。

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