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On the Use of Energy Decomposition Analyses to Unravel the Origin of the Relative Stabilities of Isomers

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On the Use of Energy Decomposition Analyses to Unravel the Origin of the Relative Stabilities of Isomers ON THE USE OF ENERGY DECOMPOSITION ANALYSES TO UNRAVEL THE ORIGIN OF THE RELATIVE STABILITIES OF ISOMERS Majid El Hamdi Lahfid Dipòsit legal: Gi. 1531-2013 http://hdl.handle.net/10803/124220 ADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al servei TDX. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs. ADVERTENCIA. El acceso a los contenidos de esta tesis doctoral y su utilización debe respetar los derechos de la persona autora. Puede ser utilizada para consulta o estudio personal, así como en actividades o materiales de investigación y docencia en los términos establecidos en el art. 32 del Texto Refundido de la Ley de Propiedad Intelectual (RDL 1/1996). Para otros usos se requiere la autorización previa y expresa de la persona autora. En cualquier caso, en la utilización de sus contenidos se deberá indicar de forma clara el nombre y apellidos de la persona autora y el título de la tesis doctoral. 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These rights affect both the content of the thesis and its abstracts and indexes. 1 2 Doctoral thesis: On the use of energy decomposition analyses to unravel the origin of the relative stabilities of isomers Majid El Hamdi Lahfid 2013 Programa de Doctorat en Ciències Experimentals i Sostenibilitat Directed by: Prof. Miquel Solà i Puig Dr. Jordi Poater i Teixidor This memory has been presented to obtain the degree of international doctor by the Universitat de Girona 3 4 El professor Miquel Solà i Puig, catedràtic d’Universitat a l’àrea de Química Física de la Universitat de Girona i el doctor Jordi Poater i Teixidor, investigador Ramón y Cajal a l’Institut de Química Computacional i Catàlisi de la Universitat de Girona, CERTIFIQUEM: Que aquest treball titulat “On the use of energy decomposition analyses to unravel the origin of the relative stabilities of isomers”, que presenta en Majid El Hamdi Lahfid per a l’obtenció del títol de Doctor, ha estat realitzat sota la nostra direcció i que compleix els requeriments per a poder optar a la Menció Internacional. Signatura Prof. Miquel Solà i Puig Dr. Jordi Poater i Teixidor Girona, 5 6 A la meva família: la meva mare, el meu pare, els meus germans, les meves germanes, la meva àvia, els meus oncles, les meves ties A tots vosaltres 7 8 Agraïments M'agradaria donar les gràcies a Déu que em va donar la gràcia i el privilegi de seguir aquesta tesi i completar-la amb èxit malgrat els molts desafiaments que he hagut d’afrontar. En primer lloc he d’agrair especialment al Dr. Miquel Solà. Li agraeixo moltíssim la paciència, l’entusiasme i l’interès que sempre ha mostrat. Sempre aprenc un munt de coses i per qualsevol problema que pugui sorgir sempre té una bona solució. Moltes gràcies per tota l’ajuda Miquel!!! Gràcies tant des d’un punt de vista acadèmic com personal, perquè avui puc optar al grau de doctor en Química, títol amb el qual tant de temps he estat somniant. Seguint amb la supervisió de la tesi, en aquest punt també he d’agrair al Prof. Jordi Poater, l’altre co-director de la meva tesi, no sé què faria sense l’ajuda d’en Jordi, el gran avanç en la realització d’aquesta tesi ha estat gràcies a ell. Valoro molt la paciència que tens, les ganes de treballar, també l’interès i el suport. Moltes gràcies Jordi per les teves explicacions, per la qualitat científica. Gràcies tant des d’un punt de vista acadèmic com personal. També agraeixo al Ministerio de Educación i Ciencia la concessió d'una beca predoctoral per la Formació de Personal Investigador (FPI) que ha permès finançar la realització d'aquesta tesi. Ara em toca agrair a tots aquells membres de l’IQC, passats i presents, amb els quals he compartit un munt de coses durant aquest temps. Primer de tot, gràcies als companys de despatx, sinó amics, que m’han hagut d’aguantar en el dia a dia: Eloy, Lluís, Marc, Sílvia, Yevhen, Eduard, Marcel, Verònica, Carles, Pedro, Anna, Quansong, Laia, Sergi, Luz, Cristina, David, Albert, Rafa i Mikael Johansson. També a tota la nova generació d’iqccians: Joaquim Antolin, Mauricio, Abril, Juan Pablo, Erik, Ouissam,... També agraeixo de cor a la Carme de l’IQCC per tota l’ajuda des de la meva arribada a Girona, per les xerrades que feiem al seu despatx. Un gran agraïment també a en Dani que ha reparat el meu ordinador diverses vegades i m'ha facilitat l’acccés a les màquines de l’IQCC. També vull agrair als molts col.laboradors externs que han contribuït als resultats presentats en aquest manuscrit, i que sovint em van donar la benvinguda als seus equips el que em va permetre aprendres moltes noves tècniques. Finalment, vull donar les gràcies a tots els membres de l’IQCC que han aconseguit que aquests anys de tesi hagin estat molt agradables. 9 No em puc oblidar de la resta d’excompanys experimentals i els actuals, amb els que també hem compartit molts moments durant les celebracions o sopars: Rafael, Montse, Marc Font, Jordi, Magdalena,.... Sortint del món químic...hi ha un munt de gent que m’ha acompanyat durant aquests anys de la meva vida i els quals m’han donat suport. Sobretot he d’agrair a la meva mare, qui sempre m’ha donat una empenta i ànims per tal que arribés el dia d’avui i obtenir aquestes dues lletres. Finalment, moltíssimes gràcies als meus germans, les meves germanes, la meva àvia, ties, i oncles pel seu suport incondicional sempre. I per acabar, moltíssimes gràcies el meu cosí Abdellatif i també company meu d’ estudis durant molts anys. Hem compartit molts moments majoritàriament de diligència i perseverança (estudis, participar en els concursos, buscant beques o treball, ....). Així mateix, no m'he oblidat de les teves ajudes durant els moments difícils. Has estat l'amic lleial i el gran germà compassiu. Moltes gràcies per tota l'ajuda que m’has proporcionat!! Moltes gràcies a tots els que han contribuït al meu èxit. El Hamdi Lahfid, Majid 10 Table of Contents Summary ...................................................................................................................................... 15 Resum ........................................................................................................................................... 17 Resumen ....................................................................................................................................... 19 Full List of Publications .............................................................................................................. 23 List of Acronyms ......................................................................................................................... 27 List of Figures .............................................................................................................................. 29 List of Tables ................................................................................................................................ 31 List of Schemes ............................................................................................................................ 33 Chapter 1: General Introduction ............................................................................................... 37 1. Introduction .......................................................................................................................... 39 1.1 The chemical bond definition .......................................................................................... 40 1.2 Types of Chemical Bonds ................................................................................................ 41 1.2.1 Strong chemical bond ..................................................................................................... 41 1.2.1.1 The covalent bond ..................................................................................................
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