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脂肪族聚酰胺通过基态与激发态之间的锥形交叉的光降解途径

Photodegradation Pathways of Aliphatic Polyamide through Conical Intersection between Ground and Excited States.

作者信息

Sang Jingcheng, Orimoto Yuuichi, Aoki Yuriko

机构信息

Department of Interdisciplinary Engineering Sciences, Chemistry and Materials Science, Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasuga Park, Fukuoka 816-8580, Japan.

Department of Material Sciences, Faculty of Engineering Sciences, Kyushu University, 6-1 Kasuga Park, Fukuoka 816-8580, Japan.

出版信息

J Phys Chem A. 2024 Oct 17;128(41):8865-8877. doi: 10.1021/acs.jpca.4c03615. Epub 2024 Oct 2.

DOI:10.1021/acs.jpca.4c03615
PMID:39358900
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11492239/
Abstract

Time-dependent density functional theory studies were performed to investigate the photochemistry properties of the widely used aliphatic polyamide (APA), alias nylon, under ultraviolet radiation with -ethylacetamide (NEA) being the model molecule. The characteristics of the transition molecular orbitals for the low-order excited states (ESs) of NEA were clarified, and the ES geometries related to the transition worthy of study were optimized. Our research proved that there is a conical intersection between the ground and excited states featured by the transition from the lone pair orbital to the σ antibonding orbital on the C-N bond within the peptide group or the N-C bond adjacent to the carbonyl group, and the C-N or N-C bond has the probability to be disrupted after internal conversion. These original quantum chemistry discoveries depict the C-N and N-C bond cleavage scheme that initiates the primary and secondary paths in the scission processes of the APA chain, respectively, which is helpful for giving new insight into the overall photodissociation mechanism of APA and designing advanced polyamide-based synthetic fibers.

摘要

进行了含时密度泛函理论研究，以考察广泛使用的脂肪族聚酰胺（APA，别名尼龙）在紫外线辐射下的光化学性质，以N - 乙基乙酰胺（NEA）作为模型分子。阐明了NEA低阶激发态（ESs）的跃迁分子轨道特征，并优化了与值得研究的跃迁相关的ES几何结构。我们的研究证明，在肽基内C - N键或羰基相邻的N - C键上，基态与激发态之间存在锥形交叉，其特征是从孤对轨道跃迁到σ反键轨道，并且C - N或N - C键在内部转换后有被破坏的可能性。这些原始的量子化学发现分别描绘了引发APA链断裂过程中一级和二级路径的C - N和N - C键断裂方案，这有助于深入了解APA的整体光解离机理，并设计先进的聚酰胺基合成纤维。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f2e7/11492239/121e032484a2/jp4c03615_0008.jpg
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