{"id":{"repo_id":"chile","oai_identifier":"oai:repositorio.uchile.cl:2250/192174"},"canonical_url":"https://search.dev.ndltd.org/etd/chile/oai:repositorio.uchile.cl:2250/192174","repository":{"repo_id":"chile","name":"Universidad de Chile","base_url":"https://repositorio.uchile.cl/oai/request"},"display":{"title":"Indices de reactividad y selectividad para caracterizar moléculas, clusters y reacciones químicas","abstract":"Potential energy surface is a key concept in the application of electronic structure methods to the study of molecular structure, properties and reactivities, however its determination imply a high computational cost. The aim of this work is to apply the concepts and principles based upon Density Functional Theory to the study of molecules, chemical reactions and copper clusters and to propose theoretical models of chemical reactivity from the calculation of specific portions of the potential energy surface. It is shown that principles of chemical reactivity and descriptors based on DFT are operative for characterizing and rationalizing the electronic properties of molecular systems and reactions. The conceptual classical model in which a reaction proceeds from one energy minimum to another via an intermediate maximum, together with the Principles of Maximun Hardness and Minimum Polarizability provide the necessary elements to discuss the activation and relaxation processes in terms of the activation chemical potential and chemical hardness. On the other hand the Sanderson's geometric equalization principle for electronegativity has been used to derive expressions for molecular hardness and its derivative, in this context, a new scheme for obtaining molecular properties from the isolated fragments is proposed with results that are in excellent agreement with others addition schemes. The formation reactions of copper clusters have been studied from the available experimental data of binding energy and DFT-descriptors and very useful relationship between energy and electronic properties are proposed to characterize the growth pattern of copper clusters.","abstract_html":"Potential energy surface is a key concept in the application of electronic structure methods to the study of molecular structure, properties and reactivities, however its determination imply a high computational cost. The aim of this work is to apply the concepts and principles based upon Density Functional Theory to the study of molecules, chemical reactions and copper clusters and to propose theoretical models of chemical reactivity from the calculation of specific portions of the potential energy surface. It is shown that principles of chemical reactivity and descriptors based on DFT are operative for characterizing and rationalizing the electronic properties of molecular systems and reactions. The conceptual classical model in which a reaction proceeds from one energy minimum to another via an intermediate maximum, together with the Principles of Maximun Hardness and Minimum Polarizability provide the necessary elements to discuss the activation and relaxation processes in terms of the activation chemical potential and chemical hardness. On the other hand the Sanderson's geometric equalization principle for electronegativity has been used to derive expressions for molecular hardness and its derivative, in this context, a new scheme for obtaining molecular properties from the isolated fragments is proposed with results that are in excellent agreement with others addition schemes. The formation reactions of copper clusters have been studied from the available experimental data of binding energy and DFT-descriptors and very useful relationship between energy and electronic properties are proposed to characterize the growth pattern of copper clusters.","abstract_has_math":false,"creators":["Jaque Olmedo, Pablo Cesar"],"institution":"Universidad de Chile","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Toro Labbé, Alejandro"],"committee_chairs":[],"committee_members":[],"year":2003,"date_issued":"2003","date_published":"2003","updated_at":"2026-07-27T19:10:18Z","subjects":["Reactividad química","Reacciones químicas"],"languages":["es"],"rights":["Attribution-NonCommercial-NoDerivs 3.0 United States"],"rights_urls":["http://creativecommons.org/licenses/by-nc-nd/3.0/us/"],"identifier_entries":[]},"links":{"outbound_url":"https://repositorio.uchile.cl/handle/2250/192174","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Toro Labbé, Alejandro"]},{"key":"dc:creator","label":"Author","values":["Jaque Olmedo, Pablo Cesar"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2023-03-16T20:32:28Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2023-03-16T20:32:28Z"]},{"key":"dc:date.issued","label":"Date","values":["2003"]},{"key":"dc:publisher","label":"Institution","values":["Universidad de Chile"]},{"key":"dc:type","label":"Dc Type","values":["Tesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Reactividad química","Reacciones químicas"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["es"]},{"key":"dc:rights","label":"Dc Rights","values":["Attribution-NonCommercial-NoDerivs 3.0 United States"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://creativecommons.org/licenses/by-nc-nd/3.0/us/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://repositorio.uchile.cl/handle/2250/192174"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Potential energy surface is a key concept in the application of electronic structure methods to the study of molecular structure, properties and reactivities, however its determination imply a high computational cost. The aim of this work is to apply the concepts and principles based upon Density Functional Theory to the study of molecules, chemical reactions and copper clusters and to propose theoretical models of chemical reactivity from the calculation of specific portions of the potential energy surface. It is shown that principles of chemical reactivity and descriptors based on DFT are operative for characterizing and rationalizing the electronic properties of molecular systems and reactions. The conceptual classical model in which a reaction proceeds from one energy minimum to another via an intermediate maximum, together with the Principles of Maximun Hardness and Minimum Polarizability provide the necessary elements to discuss the activation and relaxation processes in terms of the activation chemical potential and chemical hardness. On the other hand the Sanderson's geometric equalization principle for electronegativity has been used to derive expressions for molecular hardness and its derivative, in this context, a new scheme for obtaining molecular properties from the isolated fragments is proposed with results that are in excellent agreement with others addition schemes. The formation reactions of copper clusters have been studied from the available experimental data of binding energy and DFT-descriptors and very useful relationship between energy and electronic properties are proposed to characterize the growth pattern of copper clusters.","El concepto de superficie de energía potencial es clave en la aplicación de métodos de estructura electrónica al estudio de estructuras moleculares, propiedades y reactividades, sin embargo su determinación implica un alto costo computacional. El objetivo de este trabajo es aplicar los conceptos y principios que están basados en la Teoría Funcional de la Densidad al estudio de moléculas, reacciones químicas y clusters de cobre y proponer modelos teóricos de reactividad química a partir del cálculo de porciones específicas de la superficie de energía potencial. Es mostrado que los principios de reactividad química y descriptores basados sobre la TFD son de utilidad para caracterizar y racionalizar propiedades electrónicas de sistemas moleculares y reacciones químicas. El modelo conceptual clásico que procede a partir de un mínimo de energía a otro via un intermediario cuya energía es máxima junto a los Principios de Máxima Dureza y Mínima Polarizabilidad proveen los elementos necesarios para discutir los procesos de activación y relajación en términos de potencial químico y dureza química de activación. Por otra parte, el principio del promedio geométrico de la electronegatividad de Sanderson's ha sido utilizado como base para derivar expresiones para dureza molecular y su derivada, en este contexto, se ha propuesto un nuevo esquema para obtener propiedades moleculares a partir de fragmentos aislados con resultados que están en excelente acuerdo con otros esquemas de aditividad. Las reacciones de formación de clusters de cobre han sido estudiadas a partir de datos experimentales de energías de enlace y propiedades electrónicas y descriptores-TFD y se han propuesto relaciones entre energía y propiedades electrónicas que son de gran utilidad para caracterizar patrones de crecimiento de clusters de cobre."]},{"key":"dc:title","label":"Title","values":["Indices de reactividad y selectividad para caracterizar moléculas, clusters y reacciones químicas"]}]}],"canonical_facts":{"dc:contributor.advisor":["Toro Labbé, Alejandro"],"dc:creator":["Jaque Olmedo, Pablo Cesar"],"dc:date.accessioned":["2023-03-16T20:32:28Z"],"dc:date.available":["2023-03-16T20:32:28Z"],"dc:date.issued":["2003"],"dc:description.abstract":["Potential energy surface is a key concept in the application of electronic structure methods to the study of molecular structure, properties and reactivities, however its determination imply a high computational cost. The aim of this work is to apply the concepts and principles based upon Density Functional Theory to the study of molecules, chemical reactions and copper clusters and to propose theoretical models of chemical reactivity from the calculation of specific portions of the potential energy surface. It is shown that principles of chemical reactivity and descriptors based on DFT are operative for characterizing and rationalizing the electronic properties of molecular systems and reactions. The conceptual classical model in which a reaction proceeds from one energy minimum to another via an intermediate maximum, together with the Principles of Maximun Hardness and Minimum Polarizability provide the necessary elements to discuss the activation and relaxation processes in terms of the activation chemical potential and chemical hardness. On the other hand the Sanderson's geometric equalization principle for electronegativity has been used to derive expressions for molecular hardness and its derivative, in this context, a new scheme for obtaining molecular properties from the isolated fragments is proposed with results that are in excellent agreement with others addition schemes. The formation reactions of copper clusters have been studied from the available experimental data of binding energy and DFT-descriptors and very useful relationship between energy and electronic properties are proposed to characterize the growth pattern of copper clusters.","El concepto de superficie de energía potencial es clave en la aplicación de métodos de estructura electrónica al estudio de estructuras moleculares, propiedades y reactividades, sin embargo su determinación implica un alto costo computacional. El objetivo de este trabajo es aplicar los conceptos y principios que están basados en la Teoría Funcional de la Densidad al estudio de moléculas, reacciones químicas y clusters de cobre y proponer modelos teóricos de reactividad química a partir del cálculo de porciones específicas de la superficie de energía potencial. Es mostrado que los principios de reactividad química y descriptores basados sobre la TFD son de utilidad para caracterizar y racionalizar propiedades electrónicas de sistemas moleculares y reacciones químicas. El modelo conceptual clásico que procede a partir de un mínimo de energía a otro via un intermediario cuya energía es máxima junto a los Principios de Máxima Dureza y Mínima Polarizabilidad proveen los elementos necesarios para discutir los procesos de activación y relajación en términos de potencial químico y dureza química de activación. Por otra parte, el principio del promedio geométrico de la electronegatividad de Sanderson's ha sido utilizado como base para derivar expresiones para dureza molecular y su derivada, en este contexto, se ha propuesto un nuevo esquema para obtener propiedades moleculares a partir de fragmentos aislados con resultados que están en excelente acuerdo con otros esquemas de aditividad. Las reacciones de formación de clusters de cobre han sido estudiadas a partir de datos experimentales de energías de enlace y propiedades electrónicas y descriptores-TFD y se han propuesto relaciones entre energía y propiedades electrónicas que son de gran utilidad para caracterizar patrones de crecimiento de clusters de cobre."],"dc:identifier.uri":["https://repositorio.uchile.cl/handle/2250/192174"],"dc:language.iso":["es"],"dc:publisher":["Universidad de Chile"],"dc:rights":["Attribution-NonCommercial-NoDerivs 3.0 United States"],"dc:rights.uri":["http://creativecommons.org/licenses/by-nc-nd/3.0/us/"],"dc:subject":["Reactividad química","Reacciones químicas"],"dc:title":["Indices de reactividad y selectividad para caracterizar moléculas, clusters y reacciones químicas"],"dc:type":["Tesis"]},"updated_at":"2026-07-27T19:10:18Z"}