The Relative Intensities of Fluorescence and Phosphorescence in Biacetyl Vapor1
The Relative Intensities of Fluorescence and Phosphorescence in Biacetyl Vapor1
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联乙酰蒸气中荧光和磷光的相对强度1
DOI：
10.1021/ja01561a006
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发表时间：
1957
影响因子：
15
通讯作者：
W. Noyes
中科院分区：
文献类型：
--
作者：
H. Okabe;W. Noyes
当激发波长分别为4358和3650 A左右时，描述了一种测量双乙酰基蒸汽在光谱的蓝色（荧光）和绿色（磷光）部分发射的相对强度的技术。在26和42毫米压力下的纯双乙酰中，绿色与蓝色的综合比为58（±8）：1。该比值不受波长变化和丙酮、苯或氯甲烷加入的影响。该比值随着温度的升高而降低，在加入氧气后迅速降至零。产生磷光的状态必须由产生荧光的电子振动状态通过一个与荧光平行且独立于荧光的步骤形成。在所研究的条件下，这两种速率显然必须与碰撞无关。解离必须发生在单重态的较高振动水平，尽管数据没有提供关于这一过程细节的结论。在3130A辐照下，双乙酰基-丙酮混合物的双乙酰基发射。（主要被丙酮吸收）在室温下会优先激发磷光而不是荧光。先前提出的机制可以解释这些事实。
A technique is described for measuring the relative intensities of emission from biacetyl vapor in the blue (fluorescence) and in the green (phosphorescence) parts of the spectrum when exciting wave lengths are around 4358 and 3650 A., respec-tively. In pure biacetyl at 26 and 42 mm. pressure the integrated ratio of green to blue is 58 (±8): 1. This ratio is unaffected by change in wave length and by the addition of acetone, benzene or methyl chloride. The ratio decreases as the temperature is raised and decreases rapidly to zero upon addition ofoxygen. The state from which phosphorescence occurs must be formed from the electronic-vibration state from which fluorescence occurs by a step which parallels and is inde-pendent of fluorescence. Both rates must apparently be collision independent under the conditions studied. Dissociation must occur from upper vibration levels of the singlet state although the data do not provide conclusions about details of this process. Biacetyl emission inbiacetyl-acetone mixtures irradiated at 3130A.(absorbed mainly bythe acetone) leads at room temperature to a preferential excitation of phosphorescence rather than fluorescence. Thepreviously proposed mechanism can account for these facts.