How Vibrational Notations Can Spoil Infrared Spectroscopy: A Case Study on Isolated Methanol

IF 3.7 Q2 CHEMISTRY, PHYSICAL
Dennis F. Dinu*, Kemal Oenen, Jonas Schlagin, Maren Podewitz, Hinrich Grothe, Thomas Loerting and Klaus R. Liedl, 
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引用次数: 0

Abstract

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.

振动符号如何破坏红外光谱学?隔离甲醇案例研究
一个世纪以来,揭示甲醇的红外光谱一直是光谱学家们面临的挑战,还有许多问题有待探索。我们根据在固体氩气和氖气基质中分离单个甲醇分子的实验进行了这一探索。我们报告了天然同位素组成的甲醇以及部分氘化和完全氘化甲醇的红外光谱。在进行这些实验的同时,我们还根据振动构型相互作用方法计算了涉及非谐波和模态耦合的波数。这样就能明确分配中红外光谱中的所有基频和共振。随着氘化程度的增加,共振也会随之增加,并有助于唯一地分配波段。此外,我们还发现,化学或物理学中通常用于描述光谱中分子振动的不同符号未能恰当地描述光谱。我们强调了这些缺陷,并建议使用桑基图进行更精细的分析,以明确识别光谱特征。因此,我们揭开了甲基的各种延伸和变形所产生的共振的神秘面纱。
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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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