MAGNETIC-FIELD EFFECTS ON CHEMILUMINESCENT FLUID SOLUTIONS
MAGNETIC-FIELD EFFECTS ON CHEMILUMINESCENT FLUID SOLUTIONS
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DOI：
10.1080/00268977500100801
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发表时间：
1975-01-01
影响因子：
1.7
通讯作者：
EVANS, GT
中科院分区：
文献类型：
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作者：
ATKINS, PW;EVANS, GT
计算了磁场对流体溶液中化学发光反应产生的荧光强度的影响。计算首先考虑在彼此附近旋转的三线态分子对，并计算磁场对整个单线态的填充速率的影响。与固态情况下一样，磁场会降低这一比率。然后，允许三元组扩散分开，并且填充该对的整体单线态的过程被视为在扩散轨迹期间发生的松弛过程。在这种情况下，在高场下，强度也会减弱。对三重态-双重态的猝灭进行了重复计算，与固体结果一致，在高场下增强了强度，这是因为双重态-三重态碰撞的猝灭速度减小了，所产生的荧光是通过逃脱失败的D-T相遇的三重态而产生的。给出了涉及流体动力学参数(如溶液中物种的平移关联时间和转动关联时间)的荧光强度的显式表达式。
The effect of a magnetic field on the intensity of fluorescence from chemiluminescent reactions occurring in fluid solutions is calculated. The calculation first considers pairs of triplet molecules rotating in each other's vicinity and calculates the effect of a magnetic field on the rate at which the overall singlet state is populated. The field diminishes this rate, as in the solid-state situation. The triplets are then allowed to diffuse apart, and the process of populating the overall singlet state of the pair is treated as a relaxation process occurring during the diffusive trajectory. In this case too at high fields the intensity diminishes. The calculations are repeated for triplet-doublet quenching, and, in accord with the solid-state results, the intensity is enhanced at high fields because the quenching rate for doublet-triplet collisions is diminished, and the resultant fluorescence arises via triplets which escape abortive D-T encounters. Explicit expressions involving the dynamical parameters of the fluid (e.g. the translational and rotational correlation times of the species in the solutions) are given for the fluorescence intensity.