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级联光学过程的影响:第二部分:对样品吸收和散射特性实验量化的影响

Effects of Cascading Optical Processes: Part II: Impacts on Experimental Quantification of Sample Absorption and Scattering Properties.

作者信息

Wathudura Pathum, Wamsley Max, Wang Ankai, Chen Kexun, Nawalage Samadhi, Wang Hui, Zou Shengli, Zhang Dongmao

机构信息

Department of Chemistry, Mississippi State University, Mississippi State, Mississippi 39759, United States.

Department of Chemistry, University of Central Florida, Orlando, Florida 32816, United States.

出版信息

Anal Chem. 2023 Mar 7;95(9):4461-4469. doi: 10.1021/acs.analchem.2c05055. Epub 2023 Feb 14.

Abstract

In Part I of the three companion articles, we reported the effects of light scattering on experimental quantification of scattering extinction, intensity, and depolarization in solutions that contain only scatterers with no significant absorption and photoluminescence activities. The present work (Part II) studies the effects of light scattering and absorption on a series of optical spectroscopic measurements done on samples that contain both absorbers and scatterers, but not emitters. The experimental UV-vis spectrum is the sum of the sample absorption and scattering extinction spectra. However, the upper limit of the experimental Beer's-law-abiding extinction can be limited prematurely by the interference of forward scattered light. Light absorption reduces not only the sample scattering intensity but also the scattering depolarization. The impact of scattering on sample light absorption is complicated, depending on whether the absorption of scattered light is taken into consideration. Scattering reduces light absorption along the optical path length from the excitation source to the UV-vis detector. However, the absorption of the scattered light can be adequate to compensate the reduced light absorption along such optical path, making the impacts of light scattering on the sample total light absorption negligibly small (<10%). The latter finding constitutes a critical validation of the integrating-sphere-assisted resonance synchronous spectroscopic method for experimental quantification of absorption and scattering contribution to the sample UV-vis extinction spectra. The techniques and general guidelines provided in this work should help improve the reliability of optical spectroscopic characterization of nanoscale or larger materials, many of which are simultaneous absorbers and scatterers. The insights from this work are foundational for Part III of this series of work, which is on the cascading optical processes on spectroscopic measurements of fluorescent samples.

摘要

在三篇配套文章的第一部分中,我们报道了光散射对仅包含无显著吸收和光致发光活性的散射体的溶液中散射消光、强度和去极化实验量化的影响。本工作(第二部分)研究了光散射和吸收对一系列对同时包含吸收体和散射体但不包含发射体的样品进行的光学光谱测量的影响。实验紫外可见光谱是样品吸收光谱和散射消光光谱的总和。然而,实验中遵循比尔定律的消光上限可能会因前向散射光的干扰而过早受到限制。光吸收不仅会降低样品的散射强度,还会降低散射去极化。散射对样品光吸收的影响很复杂,这取决于是否考虑散射光的吸收。散射会降低从激发源到紫外可见探测器的光程上的光吸收。然而,散射光的吸收可能足以补偿沿该光程降低的光吸收,使得光散射对样品总光吸收的影响小到可以忽略不计(<10%)。后一发现构成了积分球辅助共振同步光谱法对样品紫外可见消光光谱中吸收和散射贡献进行实验量化的关键验证。本工作中提供的技术和一般指导方针应有助于提高对纳米级或更大尺寸材料进行光学光谱表征的可靠性,其中许多材料同时是吸收体和散射体。本工作的见解是本系列工作第三部分的基础,第三部分是关于荧光样品光谱测量中的级联光学过程。

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