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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Energy Disposal in the Photodissociation of Co(CO)_3NO near 225 nm
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Energy Disposal in the Photodissociation of Co(CO)_3NO near 225 nm

机译：Co（CO）_3NO在225 nm附近的光解中的能量处置

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摘要

The photodissociation of Co(CO)_3NO was studied near 225 nm. Apparent two-photon dissociation of the parent compound produces Co~* in a number of excited states that emit in the range of 340-360 nm. Both quartet and doublet states of Co~* are observed, implying the existence of spin-conserving and nonspin-conserving dissociation channels. Assignment of the Co~* emission is used to calculate an upper limit for the average metal-ligand bond dissociation energy of 36.2-38.6 kcal/mol with no spin-conservation restrictions and 41.2-43.9 kcal/mol with spin-conservation restrictions. The Co~* emission intensities are used to determine the relative populations of particular J and spin states and to demonstrate that J states within a particular LS configuration are statistically populated. The NO photoproduct was detected by fluorescence excitation spectroscopy. The NO appears to follow dual Boltzmann statistics with rotational temperatures of 580 ± 70 K for E_(rot) < 500 cm~(-1) and 2800 ± 300 K for E_(rot) > 500 cm~(-1).
机译：研究了Co（CO）_3NO在225 nm附近的光解离。母体化合物的表观双光子解离会产生许多激发态的Co〜*，其发射范围为340-360 nm。观察到Co〜*的四重态和双重态，这表明存在自旋和非自旋解离通道。 Co〜*发射的分配用于计算平均金属-配体键解离能的上限，其不受自旋保护的限制为36.2-38.6 kcal / mol，具有自旋保护的限制为41.2-43.9 kcal / mol。 Co *发射强度用于确定特定J和自旋态的相对种群，并证明特定LS构型内的J态在统计上得到填充。通过荧光激发光谱法检测到NO光产物。 NO似乎遵循双重玻尔兹曼统计，E_（rot）<500 cm〜（-1）的旋转温度为580±70 K，E_（rot）> 500 cm〜（-1）的旋转温度为2800±300K。

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