Gas-phase rotational analysis of non-covalent interactions in thiol and carbon dioxide aggregates
Non-covalent interactions play a crucial role in various chemical fields like supramolecular, atmospheric or biological Chemistry. For this reason, the investigation of non-covalent interactions at the molecular level is a crucial step for understanding their nature and physical properties. In this...
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| Formato: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Recursos: | Universidad de Valladolid |
| Repositorio: | UVaDOC. Repositorio Documental de la Universidad de Valladolid |
| OAI Identifier: | oai:uvadoc.uva.es:10324/75951 |
| Acesso em linha: | https://doi.org/10.35376/10324/75951 https://uvadoc.uva.es/handle/10324/75951 |
| Access Level: | acceso abierto |
| Palavra-chave: | Espectroscopia molecular Rotational Spectroscopy Espectroscopia de rotacion Non-covalent interactions Interacciones no covalentes Hydrogen bond Enlace de hidrogeno Intermolecular aggregates Agregados intermoleculares 23 Química |
| Resumo: | Non-covalent interactions play a crucial role in various chemical fields like supramolecular, atmospheric or biological Chemistry. For this reason, the investigation of non-covalent interactions at the molecular level is a crucial step for understanding their nature and physical properties. In this Thesis we have examined non-covalent interactions using weakly-bound intermolecular aggregates generated in jet-cooled supersonic expansions, with the triple objective of discerning their electronic, structural and aggregation properties. The methodology used in the Thesis combined high-resolution broadband microwave spectroscopy and quantum mechanical calculations. The molecular targets included two different chemical classes: 1) Heteroaggregates containing mono and biarenes functionalized with thiols and alcohols, and 2) Heteroaggregates containing four-membered cyclic ketones and carbon dioxide. The thiol adducts reported in the Thesis include the heterodimers of phenol-thiophenol, (1-naphthol)-(1-naphthalenethiol) and (2-naphthol)-(2-naphthalenethiol). The aggregates of carbon dioxide included the substrates of β-propiolactone and cyclobutanone, for which we studied the adducts made of up to three carbon dioxide molecules and two substrate molecules. The experiments included the spectral analysis of the rotational spectra, the quantum mechanical prediction of electronic, structural and conformational properties and the investigation of the noncovalent interactions using post-calculation tools based on the electronic density gradients, molecular orbital populations and energy decomposition analysis. The combined experimental and theoretical work provides a detailed molecular description of the intermolecular forces stabilizing the adducts, including specifically the hydrogen bond, π-π stacking and tetrel bond interactions. |
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