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Dihydrogen Bonds: a Study DIHYDROGEN BONDS: A STUDY David HUGAS GERMÀ ISBN: 978-84-694-2209-0 Dipòsit legal: GI-190-2011 http://hdl.handle.net/10803/7921 This work is licensed under the Creative Commons Attribution-NonCommercial-ShareAlike 3.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-sa/3.0/ or send a letter to Creative Commons, 171 Second Street, Suite 300, San Francisco, California, 94105, USA. Universitat de Girona Master of Science Thesis Dihydrogen Bonds: A study by David Hugas Germ`a Girona, summer 2010 Doctoral programme of\Qu´ımica te`orica i computacional" Supervisor: Dr. S´ılvia Simon Rabasseda Co-Supervisor: Prof. Dr. Miquel Duran Portas Mem`oria presentada per optar al t´ıtol de Doctor per la Universitat de Girona This work is licensed under the Creative Commons Attribution-NonCommercial-ShareAlike 3.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-sa/3.0/ or send a letter to Creative Commons, 171 Second Street, Suite 300, San Francisco, California, 94105, USA. Departament de Qu´ımica Institut de Area` de Qu´ımica F´ısica Qu´ımica Computacional La doctora S´ılvia Simon i Rabasseda, professora d'Universitat a l'Area` de Qu´ımica F´ısica de la Universitat de Girona i el professor doctor Miquel Duran i Portas, catedr`atic d'Universitat a l'Area` de Qu´ımica F´ısica de la Universitat de Girona CERTIFIQUEN QUE: En David Hugas i Germ`a, llicenciat en Qu´ımica per la Universitat de Girona, ha realitzat sota la seva direcci´o,a l'Institut de Qu´ımica Com- putacional i al Departament de Qu´ımica de la Facultat de Ci`encies de la Universitat de Girona el treball d'investigaci´oque porta per nom: \Dihydrogen Bonds: A Study" que es presenta en aquesta mem`oria per optar al grau de Doctor per la Universitat de Girona. I perqu`econsti a efectes legals, signen aquest certificat: Dra. S´ılvia Simon i Rabasseda Prof. Dr. Miquel Duran i Portas Girona, a 23 de juny de 2010 Als meus pares, als meus avis, al meu cos´ıi als meus oncles. Agra¨ıments A les mires del cel, ones ultraviolades, infraroges. Entre el submarinista i el peix que no sap on va, entre els ossos calcificats, c`el·lules. Bullen part´ıcules d'H2O al s`otil despintat, entre sistemes solars, entre l'espai perdut. L'astronauta camina amb la seguretat de saber que els ampers s´on el voltatge partit resist`encia. Camina sense escr´upols per ser com ´es, i no s'expressa [obertament perqu`eno pot. Es´ aix´ı, l'astronauta, i es mira el cel desconcertat: ones alfa, ones gamma. | Ant`onia Font C`apsula d'emerg`encia (2004) Massa temps. Cada any que passa, miro enrera i veig que la llicenciatura queda m´eslluny i que encara no he acabat el doctorat. Per`otot t´ecoses bones i dolentes. Les dolentes les deixarem per un altre dia, que si estic escrivint aquest apartat ´esque la tesi est`aa punt de comen¸car el llarg, tedi´os,feixuc i burocr`atic proc´es que acabar`a,en el menor temps possible|creuem els dits| en la seva defensa final. Llavors ja veurem qu`epassa. Amb una etapa tan llarga han passat moltes coses. I molta gent, molt´ıs- sima. De tot tipus, de molts llocs, per molts motius, de molts car`acters, de moltes relacions, coneguts per efecte directe de la recerca o coneguts pel sim- ple fet de ser viu. Ara tots ells formen part de la meva vida, encara que sigui poqu´ıssim. N'hi ha que no coneixia, n'hi ha que ja no hi son, n'hi ha que es quedaran una estona i n'hi ha que hi seran sempre. I tots ells tenen alguna cosa a veure amb mi i amb aquest compendi, i per b´eo per mal, amb major o menor mesura, m'han canviat. Me'n deixar´emolts. No m'ho tingueu en compte. Els primers de la llista s´onels meus pares. M'han animat a seguir endavant i a sortir dels sotracs amb paci`encia, afabilitat i amor. S´onels millors del M´on, encara que soni infantil. I no ´es perqu`enom´es en tingui uns! Els avis, els que hi s´oni els que no. Una em va cuidar de petit, em vestia i em feia els dinars. L'altra m'ha ensenyat a escoltar. Un em va despertar la curiositat per les coses i l'altre ´es el que em continua demostrant com ser tossut per seguir endavant. Els segons de la llista s´onels directors de tesi i els caps visibles de l'Institut de Qu´ımica Computacional. La S´ılvia Simon, que aquesta ser`a,espero, la seva primera tesi dirigida i presentada. No deixa de ser un petit honor. Tot el que hi ha aqu´ıdins i que sigui on s´oc,ella tamb´en'´es culpable. En Miquel Duran, co-director de la tesi, per tenir idees m`agiques de com orientar la recerca. En Miquel Sol`a,per haver confiat en mi a l'assignar-me la beca. I a la cap absoluta de l'IQC: La Carme L´opez. Ja sabeu com n'´esd'important una secret`aria competent en aquests llocs. No tot han sigut DHBs durant aquest temps. Altres projectes d'altra gent que han tingut m´eso menys `exit. Un dels aspectes bons del doctorat ´esla pos- sibilitat de col·laborar amb altres grups i veure altres maneres de fer. S'aprenen moltes coses, altres maneres d'organitzar-se, de treballar i de fer. La primera estada van ser tres mesos a la Universit`adi Torino, amb el professor Piero Ugliengo. Quant de temps fa d'aix`o! El temps vola. Com els articles. La segona estada va ser a Berlin, amb un tema que s´onafant`astic: \Wavepacket dynamics on conical intersections". Gr`acies a en Llu´ıs Blancafort que em va posar en contacte amb la Let´ıcia Gonz`alez a la Freie Universit¨at Berlin, ll`as- tima que no en sort´ıs res publicat, per`otant l'experi`encia professional com personal va ser extraordin`aria. I la ´ultima estada a la Vrije Universiteit Am- sterdam, amb el professor Matthias Bickelhaupt, que sap treure el suc com ning´ude qualsevol tema. Els soldats rasos que han passat pel meu costat (o jo he passat pel seu) durant tot aquest periple, que en definitiva s´onels que m'han hagut d'aguantar. Tots aquells que han passat per l'antic despatx 166 (abans una casa comunal, ara un parell de d´uplex) o voltaven per l'IQC en algun moment o altre. A veure si me'n recordo de tots: la Montse Casas (trufes!), en Miquel Torrent (pobre de mi!), en Xavier Fradera (va marxar, va tornar i va tornar a marxar), en Josep Maria Luis (escolteu les seves teories sobre parelles), en Xavier Giron´es (encara no ho entenc), en Pedro Salvador (CHA-CHA-CHA i CP), en Jordi Poater (cal tenir paci`encia per aguantar-me al costat), l'Eduard Matito (lo cavaller), l'Albert Poater (parlant d'escoltar teories...), en Quim Chaves (Zipi) i en Juanma Barroso (Zape), la Mireia Guell¨ (talons llunyans), en David Asturiol (no tothom pot ser campi´od'Espanya d'slot), la S´ılvia Osuna (divina), la Cristina Butchosa (friki fins i tot pels est`andards IQC), en Dani Mas´o(quan ´erem joves...), en Ferran Feixas (Frodo), l'Anna Dachs i l'Anna Diaz (com en Zipi i en Zape, per`oen femen´ı), l'Eloy Ramos (aquest noi ´esalt), en Sergi Ru´ız (Jap´ot'espera), la Laia Guillaumes (tu saps on et poses, piltrafilla?)... i hi han m´esnoms, que ens hem fet m´es o menys. Hi ha tot el sector experimental, envoltats de fums t`oxics i brut´ıcies estranyes que s'entossudeixen a dir-nos \raros" mentre es dediquen a treballar amb materials perillosos i contaminants. Per`oqu`ehi farem, tothom ´esfeli¸ca la seva manera. Tamb´ehi ha tota la gent que m'he anat trobant a les estades: la Marta Corno, la In´esCorral i en Willem-Jan van Zeist. Finalment, un grapat de gent que es poden contar amb els dits d'una m`a. No han desenvolupat res de la recerca, no han estat en cap article, no tenen cap ´ındex d'impacte en cap revista (b´e, alguns si) per`otenen un gran pes en tot aquest espectacle, una import`ancia fonamental per haver-me ent`es i haver- me donat `anims, girar-me els punts de vista i fer-me veure la part bona de les coses. El cam´ıamb vosaltres ´esm´esf`acil i entretingut. Gr`acies. I ara qu`em´es? List of Publications • D. Hugas, S. Simon, and M. Duran. Counterpoise-corrected potential en- ergy surfaces for dihydrogen bonded systems. Chem. Phys. Lett., 386(4{ 6):373{376, 2004. • D. Hugas, S. Simon, and M. Duran. MH ··· HX dihydrogen bond with M = Li, Na and X = F; Cl; Br: A CP-Corrected PES calculation and an AIM analysis. Struct. Chem., 16(3):257{263, 2005. • D. Hugas, S. Simon, and M. Duran. Electron density topological proper- ties are useful to assess the difference between hydrogen and dihydrogen complexes. J. Phys. Chem. A, 111(20):4506{4512, 2007. • D. Hugas, S. Simon, M. Duran, C. Fonseca Guerra, F.M. Bickelhaupt. Dihydrogen bonding: Donor-acceptor bonding (AH ··· HX) versus the H2 Molecule (A − H2 − X).
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