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激光诱导化学观察在 O 和 CHNH 混合物的 248nm 真空紫外光解过程中。

Laser-Induced Chemistry Observed during 248 nm Vacuum Ultraviolet Photolysis of an O and CHNH Mixture.

机构信息

Department of Chemistry, Emory University, Atlanta, Georgia 30322-1007, United States.

Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.

出版信息

J Phys Chem A. 2020 Dec 24;124(51):10838-10848. doi: 10.1021/acs.jpca.0c09618. Epub 2020 Dec 14.

Abstract

We present an examination of the 248 nm VUV (vacuum ultraviolet) laser photolysis of an ozone (O) and methylamine (CHNH) mixture as means to produce aminomethanol (NHCHOH). Aminomethanol is predicted to be the direct interstellar precursor to glycine and is therefore an important target for detection in the interstellar medium. However, due to its high reactivity under terrestrial conditions, aminomethanol evades gas-phase spectral detection. The insertion of O(D) into methylamine is one proposed pathway to form aminomethanol. However, this formation pathway is highly exothermic and results in a complex mixture of reaction products, complicating spectral assignment. Additional reactions between methylamine and the other products of ozone photolysis lead to further complication of the chemistry. Here, we present a systematic experimental study of these reaction pathways. We have used direct absorption millimeter/submillimeter spectroscopy in a supersonic expansion to probe the reaction products, which include formaldehyde (HCO), methanimine (CHNH), formamide (HCONH), and hydrogen cyanide (HCN) and absorption signals arising from at least two additional unknown products. In addition, we examine the effects of reaction time on the chemical formation pathways and discuss them in the context of O(D) insertion chemistry with methylamine. We have built a kinetics box model to interpret the results that are observed. We then examine the implications of these results for future studies aimed at forming and detecting aminomethanol.

摘要

我们研究了 248nm VUV(真空紫外)激光光解臭氧(O)和甲胺(CHNH)混合物,以制备氨甲醇(NHCHOH)。氨甲醇被预测为甘氨酸的直接星际前体,因此是星际介质中检测的重要目标。然而,由于其在地球条件下的高反应性,氨甲醇逃避了气相光谱检测。O(D)插入甲胺是形成氨甲醇的一种途径。然而,这种形成途径是高度放热的,导致反应产物的复杂混合物,使光谱分配复杂化。甲胺与臭氧光解的其他产物之间的进一步反应导致化学的进一步复杂化。在这里,我们对这些反应途径进行了系统的实验研究。我们使用超音速膨胀中的直接吸收毫米/亚毫米光谱学来探测反应产物,包括甲醛(HCO)、甲亚胺(CHNH)、甲酰胺(HCONH)和氢氰酸(HCN)以及至少两个未知产物的吸收信号。此外,我们还研究了反应时间对化学形成途径的影响,并在与甲胺的 O(D)插入化学的背景下对其进行了讨论。我们建立了一个动力学箱模型来解释观察到的结果。然后,我们研究了这些结果对未来旨在形成和检测氨甲醇的研究的影响。

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