ROLE OF RATE EQUATIONS IN THEORY OF LUMINESCENT ENERGY TRANSFER
ROLE OF RATE EQUATIONS IN THEORY OF LUMINESCENT ENERGY TRANSFER
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DOI：
10.1103/physrevb.4.648
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发表时间：
1971-01-01
期刊：
影响因子：
--
通讯作者：
GRANT, WJC
中科院分区：
文献类型：
--
作者：
GRANT, WJC
在本文中，我们从第一性原理，方程描述发光转移的动力学。我们应用泡利方程的适当定义的密度矩阵推导，在一个形式主义，但在相反的限制假设下，通常的非线性动力学速率方程和方程形成的起点计算的福斯特和其他人。讨论了进入这些方程的跃迁几率。结果表明，它们允许多粒子过程，如果只考虑两个粒子的过程中存在的共振的可能性大大增加。此外，在速率方程近似中，跃迁概率和产率的浓度依赖性仅反映了参与一次能量守恒转移的粒子数，而与相互作用的空间依赖性无关。这样的关联确实存在于福斯特近似，但浓度的权力和多极秩序之间的直接对应关系似乎只有在严格的约束下才有效。所观察到的非线性衰减和产量，并依赖于激发模式，很容易处理与速率方程。一些实验证据表明，速率方程近似适用于，事实上，许多系统，特别是稀土在无机主机，简要讨论。
In this paper we derive from first principles, equations describing the kinetics of luminescent transfer. We apply the Pauli equation to an appropriately defined density matrix to derive, under one formalism but under opposite limiting assumptions, both the usual nonlinear kinetic rate equations and the equations which form the starting point for the calculations of Forster and others. The transition probabilities entering these equations are discussed. It is shown that they permit multiparticle processes, with great increase in the possibility for resonances that exist if only two-particle processes are considered. Further, in the rate-equation approximation, the concentration dependence of the transition probabilities and of the yield reflects only the number of particles participating in one energy-conserving transfer, and is not associated with the spatial dependence of the interaction. Such an association does exist in the Forster approximation, but a direct correspondence between powers of concentration and multipole orders appears valid only under severe constraints. The observed nonlinearities of decays and of yields, and dependences on the excitation mode, are easily handled with rate equations. Some of the experimental evidence that the rate-equation approximation applies, in fact, to many systems, particularly to rare earths in inorganic hosts, is briefly discussed.