振动符号如何破坏红外光谱:一个分离甲醇的案例研究。

IF 3.7 Q2 CHEMISTRY, PHYSICAL
ACS Physical Chemistry Au Pub Date : 2024-10-04 eCollection Date: 2024-11-27 DOI:10.1021/acsphyschemau.4c00053
Dennis F Dinu, Kemal Oenen, Jonas Schlagin, Maren Podewitz, Hinrich Grothe, Thomas Loerting, Klaus R Liedl
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引用次数: 0

摘要

一个世纪以来,解开甲醇的红外光谱一直是光谱学家面临的挑战,还有许多未解决的问题有待探索。我们在固体氩和氖基质中分离单个甲醇分子的实验基础上进行了这一探索。我们报告甲醇的红外光谱在其自然同位素组成和部分和完全氘化。这些实验伴随着基于振动组态相互作用方法计算涉及非谐性和模式耦合的波数。这允许在中红外光谱中对所有基本原理和共振进行明确的分配。氘化程度的增加提高了共振,有助于唯一地分配谱带。同样明显的是,化学或物理中通常用于描述光谱分子振动的不同符号不能恰当地描述光谱。我们强调了缺点,并建议使用桑基图进行更详细的分析,以明确地识别光谱特征。因此,我们揭开了由甲基的各种拉伸和变形引起的有争议的共振的神秘面纱。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
How Vibrational Notations Can Spoil Infrared Spectroscopy: A Case Study on Isolated Methanol.

Unraveling methanol's infrared spectrum has challenged spectroscopists for a century, with numerous loose ends still to be explored. We engage in this exploration based on experiments of isolating single methanol molecules in solid argon and neon matrices. We report infrared spectra of methanol in its natural isotopic composition and with partial and full deuteration. These experiments are accompanied by calculating wavenumbers involving anharmonicity and mode-coupling based on the vibrational configuration interaction approach. This allows for an unambiguous assignment of all fundamentals and resonances in the mid-infrared spectrum. An increasing degree of deuteration lifts resonances and aids in assigning bands uniquely. It also becomes evident that different notations typically used in chemistry or physics to describe molecular vibration from spectroscopy fail to describe the spectra appropriately. We highlight the shortcomings and suggest a more elaborate analysis using Sankey diagrams to unambiguously identify spectral features. Consequently, we demystify debated resonances occurring from various stretches and deformations of the methyl group.

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来源期刊
CiteScore
3.70
自引率
0.00%
发文量
0
期刊介绍: ACS Physical Chemistry Au is an open access journal which publishes original fundamental and applied research on all aspects of physical chemistry. The journal publishes new and original experimental computational and theoretical research of interest to physical chemists biophysical chemists chemical physicists physicists material scientists and engineers. An essential criterion for acceptance is that the manuscript provides new physical insight or develops new tools and methods of general interest. Some major topical areas include:Molecules Clusters and Aerosols; Biophysics Biomaterials Liquids and Soft Matter; Energy Materials and Catalysis
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