RT info:eu-repo/semantics/doctoralThesis
T1 Influencia de los enlaces de halógeno en reacciones químicas de interés atmosférico
A1 Miranda, Matias Orlando
A2 Universidad de Valladolid. Escuela de Doctorado
K1 Química Atmosférica
K1 Halogen Bonds
K1 Enlaces de Halógeno
K1 Atmospheric Chemistry
K1 Química Atmosférica
K1 Reaction Mechanisms
K1 Mecanismos de Reacción
K1 Computational Chemistry
K1 Química Computacional
K1 23 Química
AB The present PhD thesis focuses on the study of the influence of halogen bonds (XBs) on chemical reactions of atmospheric interest, using tools from theoretical and computational chemistry. The initial motivation for this work lies in the importance of understanding molecular interactions to predict and explain the behaviour of chemical systems, particularly in the Earth's atmosphere, where halogens play a crucial role in processes such as ozone depletion. Throughout the thesis, several computational methods based on quantum mechanics, including density functional theory (DFT) and post-Hartree-Fock methods such as CCSD(T), are employed to analyse the electronic structure of halogenated species and the non-covalent interactions they form, especially XBs. These analyses are complemented by the study of the molecular electrostatic potential (MEP) and electron density topology to identify and characterise the stabilising interactions of interest.A detailed study of the electronic structure of atomic halogens, dihalogens, halogen monoxides and various Lewis bases of atmospheric interest reveals their ability to form XBs through the interaction between electrophilic regions (σ-holes) of the halogenated species and nucleophilic regions of the Lewis bases with which they may interact. The characterisation of several complexes stabilised by XBs has been undertaken, including those formed by dihalogens with the hydroxyl radical (X2···OH), atomic halogens with ozone (X···O3) and with carbon monoxide (X···CO). Energy decomposition analysis (EDA) provides information on the nature of the latter interactions, even suggesting the formation of an "electronic exchange channel" in the early stages of the interaction.Finally, the present study explores how the formation of XBs influences the reaction mechanisms, using halogen exchange reactions between dihalogens and the formyl radical (CHO) as a model. The results indicate that the strength of the XBs formed between the reactants can determine the presence or absence of energy barriers on the potential energy surfaces of the reactions. This finding emphasises the significance of XBs in the orientation of reactants and their potential impact on the progression of reactions in atmospheric environments.
YR 2025
FD 2025
LK https://uvadoc.uva.es/handle/10324/78043
UL https://uvadoc.uva.es/handle/10324/78043
LA spa
NO Escuela de Doctorado
DS UVaDOC
RD 15-nov-2025