Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Str. 9, D-07745 Jena, Germany; Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University, Jena D-07743, Helmholtzweg 4, Germany.
Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Str. 9, D-07745 Jena, Germany; Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University, Jena D-07743, Helmholtzweg 4, Germany.
Spectrochim Acta A Mol Biomol Spectrosc. 2019 May 15;215:345-347. doi: 10.1016/j.saa.2019.02.103. Epub 2019 Feb 27.
We present a rigorous derivation of Beer's law from electromagnetic theory which allows to establish the connection of wave optics and Maxwell's equations with quantitative UV/VIS and infrared spectroscopy. As a result of this derivation, the attenuation constant is shown to be a function of the index of refraction. For small concentrations and an index of refraction not very different from unity, however, the empirical law is retrieved. Only for very strong absorptions with attenuation constants beyond 10 l/(mol·cm) and high concentrations, noticeable deviations from the empirical law and its linear concentration dependence are predicted to occur. The derivation is presented in a form, which is not only similar to that leading to the Clausius-Mossotti equation, but also shares the same starting point. Accordingly, it can easily be included in the curricula of physical chemistry.
我们从电磁理论出发,给出了 Beer 定律的严格推导,这使得人们可以将波动光学和麦克斯韦方程组与定量的紫外/可见和红外光谱学联系起来。通过这一推导,可以看出衰减常数是折射率的函数。然而,对于小浓度和折射率与 1 相差不大的情况,会得出经验定律。只有在非常强的吸收和衰减常数超过 10 l/(mol·cm)以及高浓度的情况下,才会出现与经验定律及其线性浓度依赖性的明显偏差。这一推导采用的形式不仅与导致 Clausius-Mossotti 方程的形式相似,而且具有相同的起点。因此,它可以很容易地包含在物理化学课程中。