• Título:  ESTUDIO COMPUTACIONAL DE LA ADSORCIÓN DE MOLÉCULAS EN SUPERFICIES METÁLICAS: CARACTERIZACIÓN DE INTERACCIONES METAL-DERIVADOS DE TIOUREA
• Autor:  Barzaga Guzmán, Ransel
• Universidad:  Universidad Autónoma de Madrid
• Departamento:  Química
• Fecha de Lectura:  03/12/2021
• Mención Europeo / Mención Internacional: concedido
• Programa de doctorado:  Programa de Doctorado en Química Teórica y Modelización Computacional/Theoretical Chemistry and Computational Modelling por la Universidad Autónoma de Madrid; la Universidad Complutense de Madrid; la Universidad de Barcelona; la Universidad de Cantabria; la Universidad de Extremadura; la Universidad de las Illes Balears; la Universidad de Murcia; la Universidad de Oviedo; la Universidad de Sevilla; la Universidad de Vigo; la Universidad del País Vasco/Euskal Herriko Unibertsitatea; la Universida
• Dirección: 
  • DIAZ TENDERO, SERGIO (DIRECTOR)
  • Hernández Sánchez, Mayra Paulina (CODIRECTOR)
• Tribunal: 
  • ALCAMI PERTEJO, MANUEL (PRESIDENTE)
  • Rodriguez Gonzalez, Sandra (SECRETARIO)
  • TRUJILLO DEL VALLE, CRISTINA (VOCAL)
  • CONTRERAS GARCIA, JULIA (VOCAL)
  • González Pascual, César (VOCAL)
• Descriptores: 
  • QUIMICA
• Localización:  REPOSITORIO DE TESIS BIBLIOTECA UAM
• http://hdl.handle.net/10486/700925
• Resumen:
  In this thesis a systematic theoretical study is performed to evaluate the chemical properties of aryl/aroyl thiourea derivatives as potential building blocks of a surface nanodevice. In this functionalized nanodevice the substrate and the anchoring molecule are the fundamental building blocks. Therefore, for the prediction of potential applications understanding fundamentals aspects of the structure upon adsorption is required. It implies the individual evaluation of the interactions between environment-anchoring molecule and anchoring molecule-substrate. Thus, we devote this thesis to characterize these interactions focusing in the chemical ngerprint of the anchoring molecules. In order to do this, we have developed a computational strategy that consist on, first, a thorough search of the possible geometries that can be adopted by the anchoring molecules at the gas phase level. Secondly, from the several structures obtained multiple geometry congurations of the molecule-metal interaction are described. Next, using the electron density as the main scalar field, the evaluation of the bonding nature, electronic structure analysis, and chemical properties of the molecule-metal system is carried out. For this purpose different approaches such as Quantum Theory of Atoms in Molecule (QTAIM), topological analysis of the electron density, and charge density decomposition are used. Applying such strategy we study the complexation properties of the N;N0-aryl/aroyl thioureas with Cd(II), Hg(II) and Pb(II) cations through the analysis of the cation-molecule chemical bonding, over a set of 479 full optimized structures. Evidence of the chemoselectivity and regioselectivity of the cation-molecule binding is observed for the three cations. Subsequently, anchoring molecule-substrate interactions are investigated by the adsorption of N-monosubstituted and N;N0-disubstituted aryl/aroyl thioureas on a Au(111) surface. Gold surface is selected as substrate due to the strong Au-S chemical anity, previously addressed in others works and revisited in this thesis. N-monosubstitution of the thioureas allows us to identify the role of chemical functionalization for tuning-up the molecule adsorption geometry and surface-molecule binding strength. In the case of N,N'-disubstitution we coupled the effects of chemical functionalization to gain further insight into the molecule-surface interaction, but also, to disclose the relevance of intermolecular/molecule-surface interplay. In this way, a great variety of possible interactions between thiourea derivatives with metal has been studied; thus obtaining a complete picture of the nature of the bonds formed. This allows predicting geometric, stability and electronic properties of organosulfurized-metal hybrid materials.