一水三甲胺的oh -拉伸动力学:我们可以从三种不同的直接吸收光谱中学到什么?

IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL
Taija L. Fischer, Casper V. Jensen, Eaindra Lwin, Dhritabrata Pal, Henrik G. Kjaergaard and Martin A. Suhm
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引用次数: 0

摘要

水和三甲胺之间的氢键二元配合物的特征是射流膨胀,在室温气相和冷冻氩基体中通过其oh -拉伸基本原理。光谱比较揭示了两个波数对环境依赖性较弱的包络共振伙伴。它们单独与水弯曲泛音相对应,并与单体相对于彼此的拉伸运动相结合。环境敏感的oh -拉伸模式从室温下的组合带位置一直移动到cryommatrix隔离中的纯水弯曲泛音,其红外强度与光谱邻近度和耦合强度成比例共享。中间射流冷却光谱在很大程度上消除了热激发和嵌入效应。因此,它为理论建模提供了最简单的切入点。胺的化学和同位素取代支持了分配的稳健性,而从水到甲醇的转换则消除了基于弯曲的共振机会。经共振校正后,水配合物的羟基伸展位置与甲醇配合物非常接近。这表明甲醇和水与胺发生类似的氢键相互作用。在超声速射流和氩气基质中对水-三甲胺混合物的先前相互矛盾的光谱解释进行了讨论和劝阻。对于三甲胺二水合物,两种氢键OH拉伸振动都表现为射流膨胀。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

OH-stretching dynamics in trimethylamine monohydrate: what can we learn from three different direct absorption spectra?†

OH-stretching dynamics in trimethylamine monohydrate: what can we learn from three different direct absorption spectra?†

The hydrogen-bonded binary complex between water and trimethylamine is characterised in jet expansions, in the room temperature gas phase and in frozen argon matrices via its OH-stretching fundamental. The spectral comparison reveals two bracketing resonance partners with weak environmental dependence of their wavenumber. They correspond to the water bending overtone alone and in combination with a stretching motion of the monomers relative to each other. The environment-sensitive OH-stretching mode moves from the combination band location at room temperature all the way down to the pure water bending overtone in cryomatrix isolation, sharing its infrared intensity in proportion to the spectral vicinity and coupling strength. The intermediate jet-cooled spectrum largely removes thermal excitation and embedding effects. It thus provides the easiest entry point for theoretical modelling. Chemical and isotope substitutions at the amine support the robustness of the assignment, whereas a switch from water to methanol removes the bending-based resonance opportunities. After correction for the resonances, the OH-stretching positions of the water complex follow those of the methanol complex quite closely. This shows that methanol and water undergo similar hydrogen bond interactions with the amine. Previous contradicting spectral interpretations of water trimethylamine mixtures in supersonic jets and in argon matrices are discussed and discouraged. For the dihydrate of trimethylamine, both hydrogen-bonded OH stretching vibrations are characterised in the jet expansion.

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来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
期刊介绍: Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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