MOLECULAR DYNAMICS IN SOLUTION PROBED BY THE TRANSIENT GRATING METHOD WITH A NANOSECOND PULSED LASER

Laser Chemistry Pub Date : 1900-01-01 DOI:10.1155/1994/84218
M. Terazima, K. Okamoto, N. Hirota
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引用次数: 10

Abstract

Molecular dynamics in organic solution is investigated by the transient grating method with a nanosecond pulsed laser and a fast detection system. First, the dynamics of methyl red (MR) is studied for the probe of the translational diffusion process of solution. The origin of the TG signal which represents the mass diffusion is attributed to the phase grating created by the different refractive indices of the cis and trans forms. The cis form of MR, which has a slightly smaller molecular volume than the trans form is found to diffuse more slowly in alcoholic and aldehyde solutions. The measured diffusion coefficients (D) are compared with theoretically calculated values. Second, the TG method is applied to elucidate the dynamics of transient radicals created by photochemical reactions. The determined D of the radicals are about 3∼4 times smaller than those of the parent non-radical molecules even though the molecular volumes are similar to each other. The advantages as well as the disadvantages of the TG method for elucidating the solvent dynamics are discussed.
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用纳秒脉冲激光瞬态光栅法探测溶液中的分子动力学
利用纳秒脉冲激光和快速检测系统,采用瞬态光栅法研究了有机溶液中的分子动力学。首先,对甲基红(MR)动力学进行了研究,探讨了溶液的平移扩散过程。表示质量扩散的热重信号的来源是由顺式和变换式的不同折射率所产生的相位光栅。MR的顺式分子体积比反式分子体积略小,在酒精和醛溶液中扩散得更慢。将测量的扩散系数(D)与理论计算值进行了比较。其次,应用热重法阐明了光化学反应产生的瞬态自由基的动力学。虽然分子体积相近,但自由基的测定D值却比母体非自由基分子小3 ~ 4倍。讨论了热重法在溶剂动力学分析中的优缺点。
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